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# Weakly nonlocal continuum physics - the Ginzburg-Landau equation

## 1. Introduction

Ginzburg-Landau equation and its variants appear in different fields of physics and are applied to several phenomena. Its physical content and the way to obtain it is sound and transparent. The traditional derivation of the equation comprises two main ingredients (see e.g. )

* The static, equilibrium part of the equation is derived from a variational principle.
* The dynamic part is added by stability arguments (relaxational form).

The two parts are connected loosely and in an ad-hoc manner. As a classical field equation defined on nonrelativistic space-time, the Ginzburg-Landau equation should be compatible with the general balance and constitutive structure of continuum physics. Recently there has been several efforts to give a uniform reasoning of the equation on pure thermodynamic ground and to generalize the method of the derivation . The treatment of Ginzburg-Landau equation is a kind of test of weakly nonlocal (gradient) thermodynamic theories.

In some previous works the possible role of internal, dynamic variables in weakly nonlocal extensions of the constitutive state space was investigated both with the heuristic method of classical irreversible thermodynamics and with the more exact Liu procedure . It was found that with the help of special dynamic variables (current multipliers) appearing in a generalized entropy current one can find an equation that is similar to the Ginzburg-Landau equation, but is not the same. The equation was called thermodynamic Ginzburg-Landau equation. The static part of the Ginzburg-Landau equation gives nonhomogeneous solutions in case of uniform boundary conditions, therefore it is a pattern forming equation. On the other hand, thermodynamic Ginzburg-Landau is not a pattern forming equation, its corresponding solutions are homogeneous. This is an important difference and corresponds well to the fact that with internal variables one introduces a local theory, all the functions in the basic state space are local. Therefore any nonlocalities formulated by an internal variable theory are relocalized in this sense. Pattern forming theories, like those based on the Ginzburg-Landau equation, cannot be relocalized.

In this paper it is shown, that there is a non-equilibrium thermodynamic approach also for pattern forming equations, however, it is not relocalizable, independent of any kind of internal variables. A pure thermodynamic derivation can unify the mentioned two parts of the derivation, there is no need to postulate any kind of variational principle. The Euler-Lagrange form of the static part of the equation turns out to be a consequence of the Second Law.

In the paper the key ingredients of the methodology and the mathematical background to exploit the Second Law inequality is shortly summarized in weakly nonlocal continuum theories (gradient theories, theories with coarse grained thermodynamic potentials, phase-field models, etc..). After the introduction, an overview of the methods to exploit the Second Law inequality is given. We call the attention to the essential differences between the local and weakly nonlocal theories and a constructive way to arrive solvable Liu equations is given. The most important difference is that the weakly nonlocal extension of the constitutive state space, implies that some space derivatives of the constraints (evolution equations) are to be considered as constraints, too. A simple example show the application of Liu procedure. In the following section Liu procedure is applied to derive the Ginzburg-Landau equation. Different kind of generalizations are treated, the difference between the relocalized and pattern forming (non relocalizabile) theories is formulated. A new, generalized formulation of Liu’s theorem and its direct proof from Farkas’ lemma is given in an Appendix.

## 2. Methods to exploit the Second Law inequality - procedures of CIT, Coleman-Noll and Liu

In every non-equilibrium thermodynamic theories an important theoretical problem is to formulate the correct form of the evolution equations taking into account the requirement of the entropy inequality. The most predictive methodological solution of the problem is far from being trivial and originated from Coleman and Mizel. They essentially reverse the way of thinking: one should look for the solution of the entropy inequality taking into account the evolution equations as constraints . In continuum physics the dynamic equations are given in a determined form (e.g. as balances of extensives), except some constitutive, material functions. The task is to ensure the nonnegativity of the entropy production with appropriate constitutive assumptions. Therefore one should specify the undetermined material functions such, that in case of all possible solutions of the dynamic equations the form of the constitutive functions, the material properties, ensure the nonnegativity of the entropy production. In case of weakly nonlocal theories the entropy current plays a distinguished role. The entropy and the entropy current are both constitutive and are to be determined according to the above requirement (as it was suggested in extended rational thermodynamics ). The entropy possibly should preserve its potential character in a general sense, therefore solving the above problem (e.g. Liu equations) the practical aim is a simplification in such a way that every constitutive quantity including the entropy current could be calculated from the entropy function.

There are three basic methods to exploit the entropy inequality.

* Heuristic. This is the force-current method of classical irreversible thermodynamics (CIT). In classical problems, in case of simple state spaces, the form of the entropy production is quadratic and the inequality can be solved. The method can be justified by the Liu procedure in case of the traditional, simplest state spaces , and the method can be generalized to include non-classical entropy currents .
* Coleman-Noll procedure. In the Coleman-Noll procedure one exploits the constraints (e.g. dynamic equations) directly, substituting them into the entropy inequality. The degenerate form of Liu’s theorem (T5.5) is applied. One usually assumes a specific form of the entropy current. There are essentially two choices here. The entropy current can be the classical ($`𝐣_s=𝐣_q/T`$), or a generalized one. In weakly nonlocal considerations both classical (see e.g. ) and generalized forms are applied. Generalizations of the entropy currents (or currents of other thermodynamic potentials) can be suggested on different grounds and they give good results with the procedure  .
* Liu procedure. With Liu procedure one applies Liu’s theorem with Lagrange-Farkas multipliers (T5.3 in the Appendix). At the first glance the application of this method seems to have only practical advantages. However, as the Lagrange multiplier method preserves the simple form of the constraints in question in extremum problems, with Lagrange-Farkas multipliers one can preserve and exploit the structure of the constraint and the entropy inequality. The question is not purely mathematical, because there are cases where the multipliers cannot be eliminated and they can get physical significance. Moreover, an inevitable advantage of Liu’s method is that the structure of entropy inequality makes possible to solve completely the physical problem.

The train of thought is the following. The entropy current is considered as an independent constitutive quantity. With a proper choice of the constitutive space we can solve the Liu equations and determine the entropy current. Hence the entropy inequality simplifies considerably. The point of view of Onsagerian CIT is important here: with a proper identification of thermodynamic currents and forces the resulted entropy inequality can be solved, determining all constitutive quantities. This ensures, that our theory is independent of further artificial constraints, the entropy inequality becomes a consequence of material properties.

In weakly nonlocal continuum physical calculations with Liu procedure one should consider some additional practical rules. There the constraints are (partial) differential equations. The functions in the differential equations form the basic state space. The constitutive quantities depend on these functions, on the basic state and on some of its derivatives. These derivatives are locally independent therefore the problem is algebraically manageable. The basic state variables and some of its derivatives can be included into the constitutive state space (or simply state space ), into the domain of the constitutive functions. The entropy inequality with its special balance form determines the independent variables of the algebraic problem: those are the derivatives of the constitutive state, the so called process directions. The choice of the constitutive state space is crucial and determines the restricted constitutive functions, after applying Liu procedure. the peculiarity of weakly nonlocal theories is that depending on the particular state space, some space derivatives of the original constraints (e.g. dynamic equations) further restrict the process direction space, therefore they should be considered in Liu’s theorem as additional constraints. In the following we will show some examples to clarify the most important practical rules in the application of the formalism. One can find other examples on the application of derivative constraints in .

###### Remark 2.1.

The mentioned exploitation methods of the Second Law, being algebraic, are essentially independent of the solvability of the dynamic equations, whether the associated problems are well or ill posed, on the applied function spaces, etc… For example the number of the equations can be less than the number of variables in the basic state space. The wanted fields, the functions searched in the final resulting differential equation can be different from the basic state.

###### Example 1.

In this example the basic state space is formed by two times differentiable real functions $`x:`$. The constitutive space is spanned by the basic state and its derivative $`(x,x^{})`$. We are looking for scalar valued differentiable functions $`F`$ and $`S`$ as lying in the constitutive space so that

$$S^{}(x,x^{})0$$

for all $`(x,x^{})`$ satisfying the constraint

(1)
$$F(x,x^{})=0.$$

Evidently $`S^{}(x,x^{})=_1Sx^{}+_2Sx^{\prime \prime }`$, where $`_n`$ denotes the partial derivative according to the $`n`$-th variable. Therefore, the space of the process directions (the space of independent variables in Liu’s theorem) is spanned by $`x^{\prime \prime }`$. We are looking for conditions on $`S`$ and $`F`$ that the above inequality should be true for all $`(x,x^{})`$ solving (1), but independently of the values of $`x^{\prime \prime }`$. The degenerate case of Liu’s theorem (T5.5) gives some conditions. The single Liu equation is

$$_2S=0.$$

Therefore $`S`$ is independent on $`x^{}`$. The dissipation inequality can be written in the following simple form

(2)
$$_1Sx^{}=\frac{dS}{dx}(x)x^{}0$$

The above inequality does not give any condition for $`F`$. However, let us observe, that one of our previous assumptions was too strong. The process direction variable $`x^{\prime \prime }`$ is not really independent on the state space, the derivative of (1) gives a further restriction

(3)
$$_1Fx^{}+_2Fx^{\prime \prime }=0.$$

Considering this condition we apply Liu’s theorem (T5.3) with the multiplier method, introducing the multipliers $`\lambda _1`$ and $`\lambda _2`$ for the constraints (1) and (3) respectively

$`_1Sx^{}`$ $`+`$ $`_2Sx^{\prime \prime }\lambda _2(_1Fx^{}+_2Fx^{\prime \prime })\lambda _1F=`$
$`=`$ $`(_1S\lambda _2_1F)x^{}+(_2S\lambda _2_2F)x^{\prime \prime }\lambda _1F0`$
Therefore we can read the Liu equation as follows

$$\lambda _2_2F_2S=0$$

Expressing the multiplier and substituting into the dissipation inequality we get

$$_1Sx^{}\lambda _2_1Fx^{}\lambda _1F=(_1S_2S(_2F)^1_1F)x^{}\lambda _1F0$$

In this example we face to a partially degenerate case, hence with $`\lambda _1=0`$ we can give the general solution of the above inequality, as

$$_1S_2S(_2F)^1_1F=L(x,x^{})x^{},$$

where $`L`$ is nonnegative. Given a function $`S`$ we can calculate $`F`$, with appropriate conditions on $`L`$. For example if $`S(x,x^{})=xx^{}`$ and $`L=constant`$, then $`F(x,x^{})=f(x^{L1}x^{})`$ is a solution of the above equation for any $`f:`$.

## 3. Weakly nonlocal non-equilibrium thermodynamics – Ginzburg-Landau and thermodynamic Ginzburg-Landau equations

Let us denote an internal variable (e.g. an order parameter of a second order phase transition) characterizing the microstructure of the material by $`\xi `$. In this case the Ginzburg-Landau equation can be written as

(4)
$$_t\xi =\gamma _1\mathrm{\Gamma }_\xi +\gamma _2\mathrm{\Delta }\xi ,$$

where $`\mathrm{\Gamma }_\xi `$ is the partial derivative of the appropriate thermodynamic potential (e.g. $`\mathrm{\Gamma }_\xi =_\xi f`$, where $`f`$ is the free energy), and $`_t`$ denotes the partial time derivative. Here we assumed that the internal variable $`\xi `$ is not related to the mechanical motion, therefore the choice of the frame (partial or substantial time derivatives) is irrelevant. $`\gamma _1`$ and $`\gamma _2`$ are material coefficients. The usual form of the Ginzburg-Landau free energy density is

(5)
$$f(\xi ,\xi )=f_0(\xi )\gamma (\xi )^2/2,$$

where $`\gamma `$ is a material coefficient, $`f_0`$ is the static (equilibrium) free energy and so $`\mathrm{\Gamma }_\xi =f^{}(\xi )`$. Gurtin gave a method to deduce equation (4) from pure thermodynamic considerations, with the concept of microforce balance and showed that some additional terms should appear with a characteristic structure . The generalized form of the equation together with the characteristic term is the following

(6)
$$_t\xi =\gamma _1\mathrm{\Gamma }_\xi +\gamma _2\mathrm{\Delta }\xi +\gamma _3\mathrm{\Delta }_t\xi ,$$

Such kind of terms appear in connection of several different phenomena and not only in case of the Ginzburg-Landau equation . E. g. the Guyer-Krumhansl equation of heat conduction can be considered as a Cattaneo-Vernotte type wave heat conduction equation supplemented by a Gurtin term.

It was argued that the Ginzburg-Landau equation is the first nonlocal extension of any kind of equation for an internal variable  and its characteristic functional form can be derived from the requirement of compatibility with the Second Law, without referring to variational principles. Hence, the reason of its wide-range applicability is well founded, because any internal variable that can characterize a material structure and is independent of other requirements should fulfill a Ginzburg-Landau equation in the first nonlocal approximation. The arguments were supported by calculations based on Liu’s theorem. However, in an internal variable, completely relocalized theory one cannot derive directly (4), but only a very similar equation, that was called thermodynamic Ginzburg-Landau equation

(7)
$$_t\xi =\gamma _{T1}\mathrm{\Gamma }_\xi +\gamma _{T2}\mathrm{\Delta }\mathrm{\Gamma }_\xi ,$$

where $`\gamma _{T1}`$ and $`\gamma _{T2}`$ are material coefficients. Moreover, the entropy (free energy) was proved to be gradient independent. One can see, that the equations (4) and (7) are similar but not the same at all. The essential qualitative difference is that static (equilibrium) solutions of the thermodynamic Ginzburg-Landau equation with homogeneous boundary conditions are homogeneous but static solutions of the original Ginzburg-Landau equation with the same boundary conditions are not, they can form structures. The situation is well known and understood in superconductors. The London equation (corresponding to the thermodynamic Ginzburg-Landau) does not determine the penetration length of the magnetic field, however, the Ginzburg-Landau equation gives that .

In the following, applying Liu’s procedure with the methodology described in the previous section, we will derive the Ginzburg-Landau equations from very general assumptions and show that the Gurtin terms are consequences of pure thermodynamic considerations, without referring new concepts, like the configurational force balance or virtual power, etc..

We are looking for a dynamic equation of $`\xi `$ in the following general form

(8)
$$_t\xi =0,$$

where $``$ is a constitutive function, which form is to be restricted by the Second Law. The basic state space is spanned by $`\xi `$. Let us assume that the constitutive space is spanned by $`\xi `$, $`\xi `$ and $`^2\xi `$. In this case the entropy inequality will be

$`_ts`$ $`+`$ $`𝐣_s=`$
$`_1s_t\xi `$ $`+`$ $`_2s_t\xi +_3s:^2_t\xi +_1𝐣_s\xi +_2𝐣_s:^2\xi +_3𝐣_s:^3\xi 0.`$
One can see, that the space of the process directions (independent variables) is spanned by $`_t\xi `$, $`_t\xi `$, $`^2_t\xi `$ and $`^3\xi `$. Moreover, let us observe that these variables are not really independent, the gradient of (8) connect them. Therefore, in addition to (8) one should consider the following constraint

(9)
$$_t\xi +=_t\xi +_1\xi +_2^2\xi +_3:^3\xi =0.$$

Introducing $`\mathrm{\Gamma }_1`$ and $`\mathrm{\Gamma }_2`$ Lagrange-Farkas multipliers for the constraints (8) and (9) respectively, one can get the following Liu equations

$`_1s`$ $`=`$ $`\mathrm{\Gamma }_1,`$
$`_2s`$ $`=`$ $`\mathrm{\Gamma }_2,`$
$`_3s`$ $`=`$ $`\mathrm{𝟎},`$
$`(_3𝐣_s\mathrm{\Gamma }_2_3)^s`$ $`=`$ $`\mathrm{𝟎}.`$
Here the superscript s denotes the symmetric part of the corresponding tensor. The first two equations determine the multipliers. From the third equation follows, that the entropy does not depend on the second derivative of $`\xi `$. Taking into account these requirements one can give a solution of the fourth equation and determine the entropy current as

(10)
$$𝐣_s(\xi ,\xi ,^2\xi )=_2s(\xi ,\xi )(\xi ,\xi ,^2\xi )+𝐣_0(\xi ,\xi ).$$

For the sake of clarity we explicitly denoted the variables of the corresponding functions. With the above solution of the Liu equations the dissipation inequality can be simplified considerably

(11)
$$𝐣_0+(_2s_1s)0.$$

Assuming, that $`𝐣_00`$ one can give the general solution of the above inequality. That solution can be interpreted by the well known traditional method of irreversible thermodynamics, choosing appropriate forces and currents. Therefore, $``$ is the constitutive quantity to be determined (thermodynamic current) and it should be proportional to the given one (force)

(12)
$$_t\xi ==L(_2s_1s)$$

with a nonnegative state dependent constitutive function $`L`$. $`s(\xi ,\xi )`$ is a given entropy function (determined from static measurements). (12) is the Ginzburg-Landau equation, and one can get back the very traditional (4) form using the specific entropy functional with a form like (5) and dealing with a strictly linear theory in a thermodynamic sense, where $`L`$ is a constant function. The choice of the right thermodynamic potential (e.g. entropy or free energy) depends on the boundary conditions .

If we do not restrict the space of the independent variables by (9), by the derivative of the original constraint, then after an easy calculations one can get the following form of the dissipation inequality

(13)
$$𝐣_0(\xi ,\xi )_1s(\xi )(\xi ,\xi ,^2\xi )0.$$

The Liu equations require, that the entropy must not depend on the gradients of the basic state. However, the dissipation inequality still can be solved, if one considers two additional physical requirements, prerequisites of relocalizability .

1. $`\xi `$ is a dynamic variable in a thermodynamic sense therefore $`\xi `$ is zero in equilibrium,
2. there is no entropy flow connected to the dynamic variable if its value is zero.

It was argued that these requirements are week from a physical point of view. With these assumptions one can specify $`𝐣_0`$ in the entropy current with the Nyíri-form as $`𝐣_0(\xi ,\xi )=𝐀(\xi ,\xi )\xi `$, or equivalently $`𝐣_0(\xi ,\xi )=\widehat{𝐀}(\xi ,\xi )_\xi s`$ , according to the mean value theorem. Here the current multipliers A or $`\widehat{𝐀}`$ are constitutive functions to be determined. With the second form of $`𝐣_0`$ the dissipation inequality (13) can be solved and gives the thermodynamic Ginzburg-Landau equation (7). Introducing an additional, new dynamic variable one can recover the additional Gurtin-term in the thermodynamic Ginzburg-Landau equation . Let us observe, that the key assumption determining the form of the additional entropy current was that the entropy current should not affect the equilibrium solutions. Because the entropy is a local function in this case, the special internal variables, the current multipliers in a sense relocalize the nonlocalities.

We can apply similar reasoning in the previous non relocalizable case, too. However, first we should extend the previous constitutive state space considering a derivative one order higher then before. Therefore, let be our constitutive space spanned by $`(\xi ,\xi ,^2\xi ,^3\xi )`$. After a short calculation we can recover the validity of (11) in these new variables. The only difference is that the final constitutive quantities e.g. $`𝐣_0`$ and $`L`$ will depend on the larger constitutive state. Now we assume that $`𝐣_0`$ has the following form

$$𝐣_0(\xi ,\xi ,^2\xi )=\widehat{𝐁}(\xi ,\xi ,^2\xi )(\xi ,\xi ,^2\xi ),$$

were $`\widehat{𝐁}`$ is a current multiplier. The above form is a direct application of the requirement that the entropy current should not change the equilibrium solutions (with some minor additional restrictions on the possible constitutive dependencies). In this case the entropy production (11) is

(14)
$$\widehat{𝐁}+(\widehat{𝐁}+_2s_1s)0.$$

With two undetermined constitutive functions ($`\widehat{𝐁},`$) the inequality has a general solution, the currents and forces are determined by the constitutive dependencies. In case of isotropic materials

$`\widehat{𝐁}`$ $`=`$ $`L_1`$
$``$ $`=`$ $`L_2(\widehat{𝐁}+_2s_1s).`$
Here $`L_1`$ and $`L_2`$ are nonnegative scalar constitutive functions. $`\widehat{𝐁}`$ can be eliminated from the above equations and finally we get

(15)
$$_t\xi ==L_2(_2s_1s)+L_2(L_1_t\xi ).$$

This is the Ginzburg-Landau equation with a characteristic additional Gurtin-term.

## 4. Conclusions and discussion

The requirement of a nonnegative entropy production is a relatively strong and not a complete form of the Second Law. Strong form because it is a local requirement and other weaker formulations require only the validity of integral inequalities. Not a complete one because an increasing entropy is only a part of the physical content of the Second Law. The stability of materials in isolated systems incorporates some other conditions (e.g. concave entropy function), too . Coleman-Mizel methodology is a kind of basic philosophical requirement of a thermodynamic theory: the acceptable theories are those, where the entropy inequality is the consequence of pure material properties and independent of other elements of the theory (e.g. initial conditions) ensuring a kind of universality and some stability properties to any thermodynamic theories.

It is interesting to know, that the doubled variational-thermodynamic structure of the Ginzburg-Landau equation can be generalized considerably. That is the idea behind the General Equation for the Nonequilibrium Reversible-Irreversible Coupling (GENERIC) , where the variational part and a formalism from mechanics plays the leading role (different brackets, geometrical point of view, etc..), but both parts are represented. In this paper we unified the variational and the thermodynamic parts of the derivation of the Ginzburg-Landau equation on a pure thermodynamic ground, where we did not refer to any kind of variational principle. However, the derived static part turned out to have a complete Euler-Lagrange form. The dynamic part contains a first order time derivative therefore one cannot hope to derive it from a variational principle of Hamiltonian type . In our approach we get the ”reversible”, ”variational” part as a specific case of the thermodynamic, irreversible thinking, but one cannot hope the contrary, the irreversible part cannot be derived from a variational, reversible thinking.

Weakly nonlocal, pattern forming equations emerge in different fields of physics independently of thermodynamic argumentation. Understanding their compatibility with the Second Law can be considered as one of the most important challenges of contemporary non-equilibrium thermodynamics. In this paper it was shown that one of the most important pattern forming equations, the Ginzburg-Landau equation, is a straightforward consequence of the entropy inequality alone in a nonlocally extended constitutive space. On the other hand the outline of the mathematical background and all the key ingredients of an efficient formalism to exploit the Second Law inequality in weakly nonlocal continuum theories (gradient theories, theories with coarse grained thermodynamic potentials, phase-field models, etc..) is given.

## 5. Appendix: Liu theorem as a variant of Farkas’ lemma and some of its consequences

In 1972 Liu introduced a method of the exploitation of the entropy principle . Liu’s procedure became a basic tool to find the restrictions posed by the entropy inequality. The method is based on a linear algebraic theorem, called Liu’s theorem in the thermodynamic literature  and on an interpretation of the entropy inequality, one of the fundamental ingredients of the Second Law. Recently Hauser and Kirchner recognized that Liu’s theorem is a consequence of the fundamental theorem of linear inequalities, a famous statement of optimization theory and linear programming, the so called Farkas’ lemma . That theorem was proved first by Farkas in 1894  and independently by Minkowski in 1896 . In this appendix we formulate and generalize Liu’s theorem in a way that is best adapted for our purposes and shows the whole train of thought from Farkas’ lemma to Liu’s theorem giving a simple proof to every statement in question.

Farkas’ lemma can be formulated in several different forms, that are more or less equivalent . Here we start from a simple variant.

###### Lemma 5.1.

(Farkas) Let $`𝐚_i\mathrm{𝟎}`$ be independent vectors in a finite dimensional vector space $`𝕍`$, $`i=1\mathrm{}n`$, and $`S=\{𝐩𝕍^{}|𝐩𝐚_i0,i=1\mathrm{}n\}`$. The following statements are equivalent for a $`𝐛𝕍`$:

(i) $`𝐩𝐛0`$, for all $`𝐩S`$.

(ii) There are nonnegative real numbers $`\lambda _1,\mathrm{},\lambda _n`$ such that $`𝐛=_{i=1}^n\lambda _i𝐚_i`$.

Proof: $`S`$ is not empty. In fact, for all $`k,i\{1,\mathrm{},n\}`$ there is a $`𝐩_k𝕍^{}`$ such that $`𝐩_k𝐚_k=1`$ and $`𝐩_k𝐚_i=0`$ if $`ik`$. Evidently $`𝐩_kS`$ for all $`k`$.

$`(ii)(i)`$ $`𝐩_{i=1}^n\lambda _i𝐚_i=_{i=1}^n\lambda _i𝐩𝐚_i0`$ if $`𝐩S`$.

$`(i)(ii)`$ Let $`S_0=\{𝐲𝕍^{}|𝐲𝐚_i=0,i=1\mathrm{}n\}`$. Clearly $`\mathrm{}S_0S`$.

If $`𝐲S_0`$ then $`𝐲`$ is also in $`S_0`$, therefore $`𝐲𝐛0`$ and $`𝐲𝐛0`$ together. Therefore for all $`𝐲S_0`$ it is true that $`𝐲𝐛=0`$.

As a consequence $`𝐛`$ is in the set generated by $`\{𝐚_i\}`$, that is there are real numbers $`\lambda _1,\mathrm{},\lambda _n`$ such that $`𝐛=_{i=1}^n\lambda _i𝐚_i`$. These numbers are nonnegative, because with the previously defined $`𝐩_kS`$, $`0𝐩_k𝐛=𝐩_k_{i=1}^l\lambda _i𝐚_i=\lambda _i𝐩_k𝐚_i=\lambda _k`$ is valid for all $`k`$. $`\mathrm{}`$

###### Remark 5.1.

In the following the elements of $`𝕍^{}`$ are called independent variables and $`𝕍^{}`$ itself is called the space of independent variables. The inequality in the first statement of the lemma is called aim inequality and the nonnegative numbers in the second statement are called Lagrange-Farkas multipliers. The inequalities determining $`S`$ are the constraints.

In the calculations an excellent reminder is to use Lagrange-Farkas multipliers similarly to Lagrange multipliers in case of conditional extremum problems:

$$𝐩𝐛\underset{i=1}{\overset{n}{}}\lambda _i𝐩𝐚_i=𝐩\left(𝐛\underset{i=1}{\overset{n}{}}\lambda _i𝐚_i\right)0,𝐩𝕍^{}$$

From this form we can read out the second statement of the lemma.

###### Remark 5.2.

The original statement does not require the independency of the vectors in the constraint. We need some extra conditions and that generalization destroys the simplicity of the proof. However, we do not need this generalization in thermodynamics.

The geometric interpretation of the theorem is important and graphic: either the vector $`𝐛`$ belongs to the cone generated finitely by the vectors $`𝐚_i`$ ($`Cone(𝐚_1,\mathrm{},𝐚_n)=\{\lambda _1𝐚_1+\mathrm{}+\lambda _n𝐚_n|(\lambda _1,\mathrm{},\lambda _n)^{+n}`$), or there exists a hyperplane separating $`𝐛`$ from the cone.

### 5.1. Affine Farkas’ lemma

This generalization of the previous lemma was first published simultaneously by A. Haar and J. Farkas in the same number of the same journal, with different proofs . Later it was reproved independently by others several times (e.g. ). Here we give a simple version again.

###### Theorem 5.2.

(Affine Farkas) Let $`𝐚_i\mathrm{𝟎}`$ be independent vectors in a finite dimensional vector space $`𝕍`$ and $`\alpha _i`$ real numbers, $`i=1\mathrm{}n`$ and $`S_A=\{𝐩𝕍^{}|𝐩𝐚_i\alpha _i,i=1\mathrm{}n\}`$. The following statements are equivalent for a $`𝐛𝕍`$ and a real number $`\beta `$:

(i) $`𝐩𝐛\beta `$, for all $`𝐩S_A`$.

(ii) There are nonnegative real numbers $`\lambda _1,\mathrm{},\lambda _n`$ such that $`𝐛=_{i=1}^n\lambda _i𝐚_i`$ and $`\beta _{i=1}^n\lambda _i\alpha _i`$.

Proof: $`S_A`$ is not empty. In fact, $`\alpha _i𝐩_kS_A`$ for all $`k`$ ($`𝐩_k𝐚_k=1`$ and $`𝐩_k𝐚_i=0`$ if $`ik`$ as previously).

$`(ii)(i)`$ $`𝐩𝐛=𝐩_{i=1}^n\lambda _i𝐚_i=_{i=1}^n\lambda _i𝐩𝐚_i_{i=1}^n\lambda _i\alpha _i\beta `$.

$`(i)(ii)`$ First we will show indirectly that the first condition of lemma 5.1 is a consequence of the first condition here, that is if (i) is true then $`𝐩𝐛0`$, for all $`𝐩S`$.

Thus let us assume the contrary, hence there is $`𝐩^{}S`$, for which $`𝐩^{}𝐛<0`$. Take an arbitrary $`𝐩S_A`$, then $`𝐩+k𝐩^{}S_A`$ for all real numbers $`k`$. But now $`(𝐩+k𝐩^{})𝐛=𝐩𝐛+k𝐩^{}𝐛<\beta `$, if $`k\frac{\beta 𝐩𝐛}{𝐩^{}𝐛}`$. That is a contradiction.

Therefore, according to Farkas’ lemma (Lemma 5.1) there exist Lagrange-Farkas multipliers $`\lambda =(\lambda _1,\mathrm{},\lambda _n)^{n+}`$ such that $`𝐛=_{i=1}^n\lambda _i𝐚_i`$. Hence $`\beta inf_{pS_A}\{𝐩_{i=1}^n\lambda _i𝐚_i\}=inf_{pS_A}\{_{i=1}^n\lambda _i𝐩𝐚_i\}=_{i=1}^n\lambda _i\alpha _i`$. $`\mathrm{}`$

###### Remark 5.3.

The multiplier form is a good reminder again

$$(𝐩𝐛\beta )\underset{i=1}{\overset{n}{}}\lambda _i(𝐩𝐚_i\alpha _i)=𝐩(𝐛\underset{i=1}{\overset{n}{}}\lambda _i𝐚_i)\beta +\underset{i=1}{\overset{n}{}}\lambda _i\alpha _i0,𝐩𝕍^{}$$

.

###### Remark 5.4.

The geometric interpretation is similar to the previous one, but everything is affine.

### 5.2. Liu’s theorem

Here the constraints are equalities instead of inequalities, therefore the multipliers are not necessarily positive.

###### Theorem 5.3.

(Liu) Let $`𝐚_i\mathrm{𝟎}`$ be independent vectors in a finite dimensional vector space $`𝕍`$ and $`\alpha _i`$ real numbers, $`i=1\mathrm{}n`$ and $`S_L=\{𝐩𝕍^{}|𝐩𝐚_i=\alpha _i,i=1\mathrm{}n\}`$. The following statements are equivalent for a $`𝐛𝕍`$ and a real number $`\beta `$:

(i) $`𝐩𝐛\beta `$, for all $`𝐩S_L`$,

(ii) There are real numbers $`\lambda _1,\mathrm{},\lambda _n`$ such that

(16)
$$𝐛=\underset{i=1}{\overset{n}{}}\lambda _i𝐚_i$$

and

(17)
$$\beta \underset{i=1}{\overset{n}{}}\lambda _i\alpha _i.$$

Proof: A straightforward consequence of the previous affine form of Farkas’ lemma because $`S_L`$ can be given in a form $`S_A`$ with the vectors $`𝐚_i`$ and $`𝐚_i`$, $`i=1,\mathrm{},n`$: $`S_L=\{𝐩𝕍^{}|𝐩𝐚_i\alpha _i,\text{and}𝐩(𝐚_i)\alpha _i,i=1\mathrm{}n\}`$.

Therefore there are nonnegative real numbers $`\lambda _1^+,\mathrm{},\lambda _n^+`$ and $`\lambda _1^{},\mathrm{},\lambda _n^{}`$ such, that $`𝐛=_{i=1}^n(\lambda _i^+𝐚_i\lambda _i^{}𝐚_i)=_{i=1}^n(\lambda _i^+\lambda _i^{})𝐚_i=_{i=1}^n\lambda _i𝐚_i`$ and $`\beta _{i=1}^n(\lambda _i^+\alpha _i\lambda _i^{}\alpha _i)`$. $`\mathrm{}`$

###### Remark 5.5.

The multiplier form is a help in the applications again

$$0(𝐩𝐛\beta )\underset{i=1}{\overset{n}{}}\lambda _i(𝐩𝐚_i\alpha _i)=𝐩(𝐛\underset{i=1}{\overset{n}{}}\lambda _i𝐚_i)\beta +\underset{i=1}{\overset{n}{}}\lambda _i\alpha _i,𝐩𝕍^{}.$$

###### Remark 5.6.

In the theorem with Lagrange multipliers for a local conditional extremum of a differentiable function we apply exactly the above theorem of linear algebra after a linearization of the corresponding functions at the extremum point.

Considering the requirements of the applications we generalize Liu’s theorem to take into account vectorial constraints. First of all let us remember some well known identifications of linear algebra: $`Lin(𝕌^{},𝕍)Bilin(𝕌^{}\times 𝕍^{},)𝕍𝕌`$, where $`Bilin`$ denotes the bilinear mappings of the corresponding spaces (see e.g. ).

###### Theorem 5.4.

(vector Liu) Let $`𝐀\mathrm{𝟎}`$ in a tensor product $`𝕍𝕌`$ of finite dimensional vector spaces $`𝕍`$ and $`𝕌`$. Let $`𝛂`$ $`𝕌`$ and $`S_{VL}=\{𝐩𝕍^{}|𝐩𝐀=\alpha \}`$. The following statements are equivalent for a $`𝐛𝕍`$ and a real number $`\beta `$:

(i) $`𝐩𝐛\beta `$, for all $`𝐩S_{VL}`$.

(ii) There is a $`𝛌𝕌^{}`$ such that

(18)
$$𝐛=𝐀𝝀,$$

and

(19)
$$\beta 𝝀𝜶.$$

Proof: Let us observe that we can get back the previous form of the theorem by introducing a linear bijection $`𝐊:𝕌^n`$, a coordinatization in $`𝕌`$. Therefore, applying it for $`𝐊𝐀=(𝐀)_i=𝐚_i`$, $`𝐊𝜶=(𝜶)_i=\alpha _i`$ and $`𝐊^{}𝐀=𝐚_i^{}`$, $`𝐊^{}𝜶=\alpha _i^{}`$ we get that $`𝐛=_{i=1}^n\lambda _i𝐚_i=_{i=1}^n\lambda _i^{}𝐚_i^{}`$. Thus $`\lambda _i^{}=𝐊^1𝐊^{}\lambda _i`$. Therefore there is a $`𝝀𝕌`$, independently of the coordinatization, with the components $`\lambda _i`$ and $`\lambda _i^{}`$ in the coordinatizations $`𝐊`$ and $`𝐊^{}`$. $`\mathrm{}`$

The previously excluded degenerate case of $`𝐀=\mathrm{𝟎}`$ deserves a special attention. Now we require the validity of the aim inequality for all $`𝐩𝕍^{}`$ without any constraint. The consequences can be formulated as previously and the proof is trivial.

###### Theorem 5.5.

(degenerate Liu) The following statements are equivalent for a $`𝐛𝕍`$ and a real number $`\beta `$:

(i) $`𝐩𝐛\beta `$ for all $`𝐩𝕍^{}`$.

(ii) $`𝐛=\mathrm{𝟎}`$ and $`\beta 0`$.

###### Remark 5.7.

The practical application rule is that if $`𝐀=\mathrm{𝟎}`$ then the multiplier is zero.

###### Remark 5.8.

In continuum physics and thermodynamics the corresponding form of (18) and (19) are called Liu equation(s) and the dissipation inequality, respectively. We apply the same names for the degenerate case, too. There the Lagrange-Farkas multipliers are called simply Lagrange multipliers. Our nomenclature honors Farkas and emphasizes the difference between the two kind of multipliers. It can be important also to make a clear distinction of a similar but different nomenclature and method in variational principle construction in continuum physics .

## 6. Acknowledgements

Thanks for Raphael Hauser, Vincent Koroneos, Tamás Matolcsi and Christina Papenfuss, for valuable critical remarks and careful reading of the manuscript and for Antonio Cimmelli for interesting discussions. This research was supported by OTKA T034715 and T034603.


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# Fractional ac Josephson effect in 𝒑- and 𝒅-wave superconductors

## I Introduction

In many materials, the symmetry of the superconducting order parameter is unconventional, i.e. not $`s`$-wave. In the high-$`T_c`$ cuprates, it is the singlet $`d_{x^2y^2}`$-wave vanHarlingen . There is experimental evidence that, in the quasi-one-dimensional (Q1D) organic superconductors $`(\mathrm{TMTSF})_2\mathrm{X}`$ TMTSF , the symmetry is triplet Chaikin , most likely the $`p_x`$-wave Abrikosov82 ; Lebed , with the $`x`$ axis along the conducting chains. Experiments indicate that $`\mathrm{Sr}_2\mathrm{RuO}_4`$ has the triplet chiral $`p_x\pm ip_y`$-wave pairing symmetry Maeno .

The unconventional pairing symmetry typically results in formation of subgap Andreev bound states Andreev  on the surfaces of these superconductors Bruder . For $`d`$-wave cuprate superconductors, the midgap Andreev states were predicted theoretically in Ref. Hu  and observed experimentally as a zero-bias conductance peak in tunneling between normal metals and superconductors (see review Tanaka-review ). For the Q1D organic superconductors, the midgap states were theoretically predicted to exist at the edges perpendicular to the chains Ours1 ; Tanuma . In the chiral superconductor $`\mathrm{Sr}_2\mathrm{RuO}_4`$, the subgap surface states are expected to have a chiral energy dispersion Honerkamp98 . Their contribution to tunneling is more complicated we-Sr2RuO4  than a simple zero-bias conductance peak found for the midgap Andreev states. Various ways of observing electron edge states experimentally are discussed in Ref. we-Synth .

When two unconventional superconductors are joined together in a Josephson junction, their Andreev surface states hybridize to form Andreev bound states in the junction. These states play an important role in the Josephson current through the junction Kulik . Andreev bound states in high-$`T_c`$ junctions were reviewed in Ref. Wendin-review . The Josephson effect between two Q1D $`p_x`$-wave superconductors was studied in Refs. Tanaka-pp ; Vaccarella . Andreev reflection Andreev-reflection  at the interfaces between the A and B phases of superfluid 3He was studied in Ref. Nishida . However, Andreev bound states were not mentioned in this paper.

In the present paper, we predict a new effect for Josephson junctions between unconventional nonchiral superconductors, which we call the fractional ac Josephson effect. Suppose both superconductors forming a Josephson junction have surface midgap states originally. This is the case for the butt-to-butt junction between two $`p_x`$-wave Q1D superconductors, as shown in Fig. 1(a), and for the $`45^{}/45^{}`$ in-plane junction between two $`d`$-wave superconductors, as shown in Fig. 5(a). (The two angles indicate the orientation of the junction line relative to the $`𝒃`$ axes of each $`d_{x^2y^2}`$ superconductor.) We predict that the contribution of the hybridized Andreev bound states produces a $`4\pi `$-periodic relation between the supercurrent $`I`$ and the superconducting phase difference $`\varphi `$: $`I\mathrm{sin}(\varphi /2)`$ 2phi . Consequently, the ac Josephson effect has the frequency $`eV/\mathrm{}`$, where $`e`$ is the electron charge, $`V`$ is the applied dc voltage, and $`\mathrm{}`$ is the Planck constant. The predicted frequency is a half of the conventional Josephson frequency $`2eV/\mathrm{}`$ originating from the conventional Josephson relation $`I\mathrm{sin}\varphi `$ with the period of $`2\pi `$. Qualitatively, the predicted effect can be interpreted as follows. The Josephson current across the two unconventional superconductors is carried by tunneling of *single electrons* (rather than Cooper pairs) between the two resonant midgap states. Thus, the Cooper pair charge $`2e`$ is replaced the single charge $`e`$ in the expression for the Josephson frequency. This interpretation is also supported by the finding that, in the tunneling limit, the Josephson current is proportional to the first power (not square) of the electron tunneling amplitude Tanaka2 ; Riedel ; Barash . Possibilities for experimental observation of the fractional ac Josephson effect are discussed in Sec. V. A summary of this work is published in the conference proceedings Brazil .

The predicted current-phase relation $`I\mathrm{sin}(\varphi /2)`$ is quite radical, because every textbook on superconductivity says that the Josephson current must be $`2\pi `$-periodic in the superconducting phase difference $`\varphi `$ 2phi . To our knowledge, the only paper that discussed the $`4\pi `$-periodic Josephson effect is Ref. Kitaev  by Kitaev. He considered a highly idealized model of spinless fermions on a one-dimensional (1D) lattice with superconducting pairing on the neighboring sites. The pairing potential in this case has the $`p_x`$-wave symmetry, and midgap states exist at the ends of the chain. They are described by the Majorana fermions, which Kitaev proposed to use for nonvolatile memory in quantum computing. He found that, when two such superconductors are brought in contact, the system is $`4\pi `$-periodic in the phase difference between the superconductors. Our results are in agreement with his work. However, we formulate the problem as an experimentally realistic Josephson effect between known superconducting materials.

For completeness, we also calculate the spectrum of Andreev bound states and the Josephson current between a singlet $`s`$-wave and a triplet $`p`$-wave superconductors, as well as between two chiral $`p`$-wave superconductors Barash-chiral . In agreement with previous literature Yip ; Tanaka-sp ; Asano , we find that a Josephson current is permitted between singlet and triplet superconductors, contrary to a common misconception that it is forbidden by the symmetry difference. However, we do not find the fractional Josephson effect in these cases.

## II The basics

The spin symmetry of the Cooper pairing is classified as either singlet $`\widehat{c}_\sigma (𝒌)\widehat{c}_\sigma ^{}(𝒌)ϵ_{\sigma \sigma ^{}}\mathrm{\Delta }(𝒌)=i\widehat{\sigma }_{\sigma \sigma ^{}}^{(y)}\mathrm{\Delta }(𝒌)`$ or triplet $`\widehat{c}_\sigma (𝒌)\widehat{c}_\sigma ^{}(𝒌)i\widehat{\sigma }^{(y)}(\widehat{𝝈}𝒏)\mathrm{\Delta }(𝒌)`$ Leggett . Here $`\widehat{c}_\sigma (𝒌)`$ is the annihilation operator of an electron with the spin $`\sigma `$ and momentum $`𝒌`$; $`ϵ_{\sigma \sigma ^{}}`$ is the antisymmetric metric tensor and $`\widehat{𝝈}`$ are the Pauli matrices acting in the spin space; $`𝒏`$ is a unit vector characterizing polarization of the triplet state. In this paper, we consider only the class of triplet superconductors where the spin-polarization vector $`𝒏`$ has a uniform, momentum-independent orientation. Everywhere in the paper, except in Sec. III.6, we select the spin quantization axis $`z`$ along the vector $`𝒏`$. Then the Cooper pairing takes place between electrons with the opposite $`z`$-axis spin projections $`\sigma `$ and $`\overline{\sigma }`$: $`\widehat{c}_\sigma (𝒌)\widehat{c}_{\overline{\sigma }}(𝒌)\mathrm{\Delta }_\sigma (𝒌)`$. Because the fermion operators $`\widehat{c}`$ anticommute, the pairing potential has the symmetry $`\mathrm{\Delta }_\sigma (𝒌)=\mathrm{\Delta }_{\overline{\sigma }}(𝒌)=\pm \mathrm{\Delta }_\sigma (𝒌)`$, where the upper and lower signs correspond to the singlet and triplet cases.

We select the coordinate axis $`x`$ perpendicular to the Josephson junction plane. We assume that the interface between the two superconductors is smooth enough, so that the electron momentum component $`k_y`$, parallel to the junction plane, is a conserved good quantum number.

Electron states in a superconductor are described by the Bogoliubov operators $`\widehat{\gamma }`$, which are related to the electron operators $`\widehat{c}`$ by the following equations Zagoskin

$`\widehat{\gamma }_{n\sigma k_y}={\displaystyle 𝑑x[u_{n\sigma k_y}^{}(x)\widehat{c}_{\sigma k_y}(x)+v_{n\sigma k_y}^{}(x)\widehat{c}_{\overline{\sigma }\overline{k}_y}^{}(x)]},`$ (1)
$`\widehat{c}_{\sigma k_y}(x)={\displaystyle \underset{n}{}}[u_{n\sigma k_y}(x)\widehat{\gamma }_{n\sigma k_y}+v_{n\overline{\sigma }\overline{k}_y}^{}(x)\widehat{\gamma }_{n\overline{\sigma }\overline{k}_y}^{}],`$ (2)
where $`\overline{k}_y=k_y`$, and $`n`$ is the quantum number of the Bogoliubov eigenstates. The two-components vectors $`\psi _{n\sigma k_y}(x)=[u_{n\sigma k_y}(x),v_{n\sigma k_y}(x)]`$ are the eigenstates of the Bogoliubov-de Gennes (BdG) equation with the eigenenergies $`E_{n\sigma k_y}`$

$$\left(\begin{array}{cc}\epsilon _{k_y}(\widehat{k}_x)+U(x)& \widehat{\mathrm{\Delta }}_{\sigma k_y}(x,\widehat{k}_x)\\ \widehat{\mathrm{\Delta }}_{\sigma k_y}^{}(x,\widehat{k}_x)& \epsilon _{k_y}(\widehat{k}_x)U(x)\end{array}\right)\psi _n=E_n\psi _n,$$
(3)
where $`\widehat{k}_x=i_x`$ is the $`x`$ component of the electron momentum operator, and $`U(x)`$ is a potential. In Eq. (3) and below, we often omit the indices $`\sigma `$ and $`k_y`$ to shorten notation where it does not cause confusion.

## III Junctions between quasi-one-dimensional superconductors

In this section, we consider junctions between two Q1D superconductors, such as organic superconductors $`(\mathrm{TMTSF})_2\mathrm{X}`$, with the chains along the $`x`$ axis, as shown in Fig. 1(a). For a Q1D conductor, the electron energy dispersion in Eq. (3) can be written as $`\epsilon =\mathrm{}^2\widehat{k}_x^2/2m2t_b\mathrm{cos}(bk_y)\mu `$, where $`m`$ is an effective mass, $`\mu `$ is the chemical potential, $`b`$ and $`t_b`$ are the distance and the tunneling amplitude between the chains. The superconducting pairing potentials in the $`s`$\- and $`p_x`$-wave cases have the forms

$`\widehat{\mathrm{\Delta }}_{\sigma k_y}(x,\widehat{k}_x)`$ $`=`$ $`\{\begin{array}{cc}\sigma \mathrm{\Delta }_\beta ,& s\text{-wave},\\ \mathrm{\Delta }_\beta \widehat{k}_x/k_F,& p_x\text{-wave},\end{array}`$ (6)
where $`\mathrm{}k_F=\sqrt{2m\mu }`$ is the Fermi momentum, and $`\sigma `$ is treated as $`+`$ for $``$ and $``$ for $``$. The index $`\beta =R,L`$ labels the right ($`x>0`$) and left ($`x<0`$) sides of the junction, and $`\mathrm{\Delta }_\beta `$ acquires a phase difference $`\varphi `$ across the junction:

$$\mathrm{\Delta }_R=\mathrm{\Delta }_0e^{i\varphi },\mathrm{\Delta }_L=\mathrm{\Delta }_0.$$
(7)
The potential $`U(x)=U_0\delta (x)`$ in Eq. (3) represents the junction barrier located at $`x=0`$. Integrating Eq. (3) over $`x`$ from –0 to +0, we find the boundary conditions at $`x=0`$:

$`\psi _L=\psi _R,_x\psi _R_x\psi _L=k_FZ\psi (0),`$ (8)
$`Z=2mU_0/\mathrm{}^2k_F,D=4/(Z^2+4),`$ (9)
where $`D`$ is the transmission coefficient of the barrier.

### III.1 Andreev bound states

A general solution of Eq. (3) is a superposition of the terms with the momenta close to $`\alpha k_F`$, where the index $`\alpha =\pm `$ labels the right- and left-moving electrons:

$$\psi _{\beta \sigma }=e^{\beta \kappa x}\left[A_\beta \left(\begin{array}{c}u_{\beta \sigma +}\\ v_{\beta \sigma +}\end{array}\right)e^{i\stackrel{~}{k}_Fx}+B_\beta \left(\begin{array}{c}u_{\beta \sigma }\\ v_{\beta \sigma }\end{array}\right)e^{i\stackrel{~}{k}_Fx}\right],$$
(10)
where $`\beta =`$ for $`R`$ and $`L`$. Eq. (10) describes a subgap state with an energy $`|E|<\mathrm{\Delta }_0`$, which is localized at the junction and decays exponentially in $`x`$ within the length $`1/\kappa `$. The coefficients $`(u_{\beta \sigma \alpha },v_{\beta \sigma \alpha })`$ in Eq. (10) are determined by substituting the right- and left-moving terms separately into Eq. (3) for $`x0`$, where $`U(x)=0`$. In the limit $`k_F\kappa `$, we find

$$\eta _{\beta \sigma \alpha }=\frac{v_{\beta \sigma \alpha }}{u_{\beta \sigma \alpha }}=\frac{E+i\alpha \beta \mathrm{}\kappa v_F}{\mathrm{\Delta }_{\beta \sigma \alpha }},\kappa =\frac{\sqrt{\mathrm{\Delta }_0^2|E|^2}}{\mathrm{}v_F},$$
(11)
where $`v_F=\mathrm{}k_F/m`$ is the Fermi velocity, and

$`\mathrm{\Delta }_{\beta \sigma \alpha }`$ $`=`$ $`\{\begin{array}{cc}\sigma \mathrm{\Delta }_\beta ,& s\text{-wave},\\ \alpha \mathrm{\Delta }_\beta ,& p_x\text{-wave},\end{array}`$ (14)
with $`\mathrm{\Delta }_\beta `$ given by Eq. (7). The $`k_y`$-dependent Fermi momentum $`\mathrm{}\stackrel{~}{k}_F=\mathrm{}k_F+2t_b\mathrm{cos}(bk_y)/v_F`$ in Eq. (10) eliminates the dispersion in $`k_y`$ from the BdG equation.

Substituting Eq. (10) into the boundary conditions (8), we obtain four linear homogeneous equations for the coefficients $`A_\beta `$ and $`B_\beta `$. These equations are compatible if the determinant of the corresponding $`4\times 4`$ matrix is zero. This compatibility condition has the following form:

$`{\displaystyle \frac{(u_{+\sigma }v_\sigma v_{+\sigma }u_\sigma )(u_{+\sigma +}v_{\sigma +}v_{+\sigma +}u_{\sigma +})}{(u_{+\sigma }v_{\sigma +}v_{+\sigma }u_{\sigma +})(u_{+\sigma +}v_\sigma v_{+\sigma +}u_\sigma )}}`$
$`=1D.`$ (15)
Using the variables $`\eta `$ defined in Eq. (11), Eq. (15) can be written in a simpler form

$$\frac{(\eta _\sigma \eta _{+\sigma })(\eta _{\sigma +}\eta _{+\sigma +})}{(\eta _{\sigma +}\eta _{+\sigma })(\eta _\sigma \eta _{+\sigma +})}=1D.$$
(16)
Substituting Eq. (11) into Eq. (16), we obtain an equation for the energies of the Andreev bound states. For a given $`\sigma `$, there are two subgap states with the energies $`E_a=aE_0(\varphi )`$ labeled by the index $`a=\pm `$, where

$`E_0^{(s)}(\varphi )`$ $`=`$ $`\mathrm{\Delta }_0\sqrt{1D\mathrm{sin}^2(\varphi /2)},s\text{-}s\text{ junction},`$ (17)
$`E_0^{(p)}(\varphi )`$ $`=`$ $`\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}(\varphi /2),p_x\text{-}p_x\text{ junction}.`$ (18)
The energies (17) and (18) are plotted as functions of $`\varphi `$ in the left panels (b) and (c) of Fig. 1. Without barrier ($`D=1`$), the spectra of the $`s`$-$`s`$ and $`p_x`$-$`p_x`$ junctions are the same and consist of two crossing curves $`E=\mathrm{\Delta }_0\mathrm{cos}\varphi /2`$, shown by the thin lines in the left panel of Fig. 1(b). A nonzero barrier ($`D<1`$) affects the energies of the Andreev bound states in the $`s`$-$`s`$ and $`p_x`$-$`p_x`$ junctions in different ways. In the $`s`$-$`s`$ case, the two energy levels repel near $`\varphi =\pi `$ and form two separated $`2\pi `$-periodic branches shown by the thick lines in the left panel of Fig. 1(b). This is well known for the $`s`$-$`s`$ junctions Zagoskin ; Furusaki99 . In contrast, in the $`p_x`$-$`p_x`$ case, the two energy levels continue to cross at $`\varphi =\pi `$, and they detach from the continuum of states above $`+\mathrm{\Delta }_0`$ and below $`\mathrm{\Delta }_0`$ at $`\varphi =0`$ and $`2\pi `$, as shown in the left panel of Fig. 1(c). The absence of energy levels repulsion at $`\varphi =\pi `$ indicates that there is no matrix element between these levels in the $`p_x`$-$`p_x`$ case, unlike in the $`s`$-$`s`$ case.

As shown in Sec. IV.1, the $`45^{}/45^{}`$ junction between two $`d`$-wave superconductors is mathematically equivalent to the $`p_x`$-$`p_x`$ junction. Eq. (18) was derived for the $`45^{}/45^{}`$ junction in Refs. Tanaka1 ; Riedel ; Barash .

### III.2 dc Josephson effect in thermodynamic equilibrium

It is well known Zagoskin ; A-B  that the current carried by a quasiparticle state $`a`$ is

$$I_a=\frac{2e}{\mathrm{}}\frac{E_a}{\varphi }.$$
(19)
The two subgap states carry opposite currents, which are plotted vs. $`\varphi `$ in the right panels (b) and (c) of Fig. 1 for the $`s`$-$`s`$ and $`p_x`$-$`p_x`$ junctions. In thermodynamic equilibrium, the total current is determined by the Fermi occupation numbers $`f_a`$ of the states at a temperature $`T`$:

$$I=\frac{2e}{\mathrm{}}\underset{a=\pm }{}\frac{E_a}{\varphi }f_a=\frac{2e}{\mathrm{}}\frac{E_0}{\varphi }\mathrm{tanh}\left(\frac{E_0}{2T}\right).$$
(20)
For the $`s`$-$`s`$ junction, substituting Eq. (17) into Eq. (20), we recover the Ambegaokar-Baratoff formula AB  in the tunneling limit $`D1`$

$$I_sD\mathrm{sin}\varphi \frac{e\mathrm{\Delta }_0}{2\mathrm{}}\mathrm{tanh}\left(\frac{\mathrm{\Delta }_0}{2T}\right)=\mathrm{sin}\varphi \frac{\pi \mathrm{\Delta }_0}{2eR}\mathrm{tanh}\left(\frac{\mathrm{\Delta }_0}{2T}\right)$$
(21)
and the Kulik-Omelyanchuk formula KO  in the transparent limit $`D1`$

$$I_s\mathrm{sin}\left(\frac{\varphi }{2}\right)\frac{e\mathrm{\Delta }_0}{\mathrm{}}\mathrm{tanh}\left(\frac{\mathrm{\Delta }_0\mathrm{cos}(\varphi /2)}{2T}\right).$$
(22)
Taking into account that the total current is proportional to the number $`N`$ of conducting channels in the junction (e.g. the number of chains), we have replaced the transmission coefficient $`D`$ in Eq. (21) by the junction resistance $`R=h/2Ne^2D`$ in the normal state.

Substituting Eq. (18) into Eq. (20), we find the Josephson current in the $`p_x`$-$`p_x`$ junction in thermodynamic equilibrium:

$`I_p=\sqrt{D}\mathrm{sin}\left({\displaystyle \frac{\varphi }{2}}\right){\displaystyle \frac{e\mathrm{\Delta }_0}{\mathrm{}}}\mathrm{tanh}\left({\displaystyle \frac{\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}(\varphi /2)}{2T}}\right)`$
$`=\mathrm{sin}\left({\displaystyle \frac{\varphi }{2}}\right){\displaystyle \frac{\pi \mathrm{\Delta }_0}{\sqrt{D}eR}}\mathrm{tanh}\left({\displaystyle \frac{\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}(\varphi /2)}{2T}}\right).`$ (23)
The temperature dependences of the critical currents for the $`s`$-$`s`$ and $`p_x`$-$`p_x`$ junctions are shown in Fig. 2. They are obtained from Eqs. (21) and (23) assuming the BCS temperature dependence for $`\mathrm{\Delta }_0`$. In the vicinity of $`T_c`$, $`I_p`$ and $`I_s`$ have the same behavior. With the decrease of temperature, $`I_s`$ quickly saturates to a constant value, because, for $`D1`$, $`E_a^{(s)}\mathrm{\Delta }_0`$ (17), thus, for $`T\mathrm{\Delta }_0`$, the upper subgap state is empty and the lower one is completely filled. In contrast, $`I_p`$ rapidly increases with decreasing temperature as $`1/T`$ and saturates to a value enhanced by the factor $`2/\sqrt{D}`$ relative to the Ambegaokar-Baratoff formula (17) at $`T=0`$. This is a consequence of two effects. As Eqs. (21) and (23) show, $`I_sD`$ and $`I_p\sqrt{D}`$, thus $`I_pI_s`$ in the tunneling limit $`D1`$. At the same time, the energy splitting between the two subgap states in the $`p_x`$-$`p_x`$ junction is small compared to the gap: $`E_0^{(p)}\sqrt{D}\mathrm{\Delta }_0\mathrm{\Delta }_0`$. Thus, for $`\sqrt{D}\mathrm{\Delta }_0T\mathrm{\Delta }_0`$, the two subgap states are almost equally populated, so the critical current has the $`1/T`$ temperature dependence analogous to the Curie spin susceptibility.

Eq. (23) was derived analytically for the $`45^{}/45^{}`$ junction between two $`d`$-wave superconductors in Refs. Riedel ; Tanaka2 , and a similar result was calculated numerically for the $`p_x`$-$`p_x`$ junction in Ref. Tanaka-pp ; Vaccarella . Notice that Eq. (23) gives the Josephson current $`I_p(\varphi )`$ that is a $`2\pi `$-periodic functions of $`\varphi `$, both for $`T=0`$ and $`T0`$. This is a consequence of the thermodynamic equilibrium assumption. At $`T=0`$, this assumption implies that the subgap state with the lower energy is occupied, and the one with the higher energy is empty. As one can see in Fig. 1, the *lower* energy is always a $`2\pi `$-periodic functions of $`\varphi `$. The assumption of thermodynamic equilibrium was explicitly made in Ref. Riedel  and was implicitly invoked in Refs. Tanaka2 ; Tanaka-pp ; Vaccarella  by using the Matsubara diagram technique. In Ref. Arie , temperature dependence of the Josephson critical current was measured in the YBCO ramp-edge junctions with different crystal angles and was found to be qualitatively consistent with the upper curve in Fig. 2.

### III.3 Dynamical fractional ac Josephson effect

The calculations of the previous section apply in the static case, where a given phase difference $`\varphi `$ is maintained for an infinitely long time, so the occupation numbers of the subgap states have enough time to relax to thermodynamic equilibrium. Now let us consider the opposite, dynamical limit. Suppose a small voltage $`eV\mathrm{\Delta }_0`$ is applied to the junction, so the phase difference acquires dependence on time $`t`$: $`\varphi (t)=2eVt/\mathrm{}`$. In this case, the state of the system is determined dynamically starting from the initial conditions. Let us consider the $`p_x`$-$`p_x`$ junction at $`T=0`$ in the initial state $`\varphi =0`$, where the two subgap states (18) with the energies $`\pm E_0`$ are, correspondingly, occupied and empty. If $`\varphi (t)`$ changes sufficiently slowly (adiabatically), the occupation numbers of the subgap states do not change. In other words, the states shown by the solid and dotted lines in Fig. 1(c) remains, correspondingly, occupied and empty. The occupied state (18) produces the current (19):

$$I_p(t)=\frac{\sqrt{D}e\mathrm{\Delta }_0}{\mathrm{}}\mathrm{sin}\left(\frac{\varphi (t)}{2}\right)=\frac{\sqrt{D}e\mathrm{\Delta }_0}{\mathrm{}}\mathrm{sin}\left(\frac{eVt}{\mathrm{}}\right).$$
(24)
The frequency of the ac current (24) is $`eV/\mathrm{}`$, a half of the conventional Josephson frequency $`2eV/\mathrm{}`$. The fractional frequency can be traced to the fact that the energies Eq. (18) and the corresponding wave functions have the period $`4\pi `$ in $`\varphi `$, rather than conventional $`2\pi `$. Although at $`\varphi =2\pi `$ the spectrum in the left panel of Fig. 1(c) is the same as at $`\varphi =0`$, the occupation numbers are different: The lower state is empty and the upper state is occupied. Only at $`\varphi =4\pi `$ the occupation numbers are the same as at $`\varphi =0`$.

The $`4\pi `$ periodicity is the consequence of the energy levels crossing at $`\varphi =\pi `$. (In contrast, in the $`s`$-wave case, the levels repel at $`\varphi =\pi `$ in Fig. 1(b), thus the energy curves are $`2\pi `$-periodic.) As discussed at the end of Sec. III.1, there is no matrix element between the crossing energy levels at $`\varphi =\pi `$. Thus, there are no transitions between them, so the occupation numbers of the solid and dotted curves in Fig. 1(c) are preserved. In order to show this more formally, we can write a general solution of the time-dependent BdG equation as a superposition of the two subgap states with the time-dependent $`\varphi (t)`$: $`\psi (t)=_aC_a(t)\psi _a[\varphi (t)]`$. The matrix element of transitions between the states is proportional to $`\dot{\varphi }\psi _+|_\varphi \psi _{}=\dot{\varphi }\psi _+|_\varphi \widehat{H}|\psi _{}/(E_{}E_+)`$. We found that it is zero in the $`p_x`$-wave case, thus there are no transitions, and the initial occupation numbers of the subgap states at $`\varphi =0`$ are preserved dynamically.

As one can see in Fig. 1(c), the system is not in the ground state when $`\pi <\varphi <3\pi `$, because the upper energy level is occupied and the lower one is empty. In principle, the system might be able to relax to the ground state by emitting a phonon or a photon. At present time, we do not have an explicit estimate for such inelastic relaxation time, but we expect that it is quite long. (The other papers Riedel ; Tanaka2 ; Tanaka-pp ; Vaccarella  that *assume* thermodynamic equilibrium for each value of the phase $`\varphi `$ do not have an estimate of the relaxation time either.) To observe the predicted ac Josephson effect with the fractional frequency $`eV/\mathrm{}`$, the period of Josephson oscillations should be set shorter than the inelastic relaxation time, but not too short, so that the time evolution of the BdG equation can be treated adiabatically. Controlled nonequilibrium population of the upper Andreev bound state was recently achieved experimentally in an $`s`$-wave Josephson junction in Ref. Baselmans .

Eq. (24) can be generalized to the case where initially the two subgap states are populated thermally at $`\varphi =0`$, and these occupation numbers are preserved by dynamical evolution

$`I_p(t)`$ $`=`$ $`{\displaystyle \frac{2e}{\mathrm{}}}{\displaystyle \underset{a}{}}{\displaystyle \frac{E_a[\varphi (t)]}{\varphi }}f[E_a(\varphi =0)]`$ (25)
$`=`$ $`\mathrm{sin}\left({\displaystyle \frac{eVt}{\mathrm{}}}\right){\displaystyle \frac{\pi \mathrm{\Delta }_0}{\sqrt{D}eR}}\mathrm{tanh}\left({\displaystyle \frac{\mathrm{\Delta }_0\sqrt{D}}{2T}}\right).`$ (26)
Notice that the periodicities of the dynamical equation (26) and the thermodynamic Eq. (23) are different. The latter equation assumes that the occupation numbers of the subgap states are in instantaneous thermal equilibrium for each $`\varphi `$.

### III.4 Tunneling Hamiltonian approach

In the infinite barrier limit $`D0`$, the energies $`\pm E_0^{(p)}`$ of the two subgap states (18) degenerate to zero, i.e. they become midgap states. The wave functions (10) simplify as follows:

$`\psi _{\pm 0}`$ $`=`$ $`{\displaystyle \frac{\psi _{L0}(x)\psi _{R0}(x)}{\sqrt{2}}},`$ (27)
$`\psi _{L0}`$ $`=`$ $`\sqrt{2\kappa }\mathrm{sin}(k_Fx)e^{\kappa x}\left(\begin{array}{c}1\\ i\end{array}\right)\theta (x),`$ (30)
$`\psi _{R0}`$ $`=`$ $`\sqrt{2\kappa }\mathrm{sin}(k_Fx)e^{\kappa x}\left(\begin{array}{c}e^{i\varphi /2}\\ ie^{i\varphi /2}\end{array}\right)\theta (x).`$ (33)
Since at $`D=0`$ the Josephson junction consists of two semi-infinite uncoupled $`p_x`$-wave superconductors, $`\psi _{L0}`$ and $`\psi _{R0}`$ are the wave functions of the surface midgap states Ours1  belonging to the left and right superconductors. Let us examine the properties of the midgap states in more detail.

If $`(u,v)`$ is an eigenvector of Eq. (3) with an eigenvalue $`E_n`$, then $`(v^{},u^{})`$ for $`s`$-wave and $`(v^{},u^{})`$ for $`p`$-wave are the eigenvectors with the energy $`E_{\overline{n}}=E_n`$. It follows from these relations and Eq. (1) that $`\widehat{\gamma }_{\overline{n}\overline{\sigma }\overline{k}_y}=C\widehat{\gamma }_{n\sigma k_y}^{}`$ with $`|C|=1`$. Notice that in the $`s`$-wave case, because $`(u,v)`$ and $`(v^{},u^{})`$ are orthogonal for any $`u`$ and $`v`$, the states $`n`$ and $`\overline{n}`$ are always different. However, in the $`p`$-wave case, the vectors $`(u,v)`$ and $`(v^{},u^{})`$ may be proportional, in which case they describe the same state with $`E=0`$. The states (30) and (33) indeed have this property:

$$v_{L0}=iu_{L0}^{},v_{R0}=iu_{R0}^{}.$$
(34)
Substituting Eq. (34) into Eq. (1), we find the Bogoliubov operators of the left and right midgap states

$$\widehat{\gamma }_{L0\sigma k_y}^{}=i\widehat{\gamma }_{L0\overline{\sigma }\overline{k}_y},\widehat{\gamma }_{R0\sigma k_y}^{}=i\widehat{\gamma }_{R0\overline{\sigma }\overline{k}_y}.$$
(35)
Operators (35) correspond to the Majorana fermions discussed in Ref. Kitaev . In the presence of a midgap state, the sum over $`n`$ in Eq. (2) should be understood as $`_{n>0}+(1/2)_{n=0}`$, where we identify the second term as the projection $`𝒫\widehat{c}`$ of the electron operator onto the midgap state. Using Eqs. (34), (35), and (2), we find

$$𝒫\widehat{c}_{\sigma k_y}(x)=u_0(x)\widehat{\gamma }_{0\sigma k_y}=v_0^{}(x)\widehat{\gamma }_{0\overline{\sigma }\overline{k}_y}^{}.$$
(36)
Let us consider two semi-infinite $`p_x`$-wave superconductors on a 1D lattice with the spacing $`l`$, one occupying $`x\overline{l}=l`$ and another $`xl`$. They are coupled by the tunneling matrix element $`\tau `$ between the sites $`\overline{l}`$ and $`l`$:

$$\widehat{H}_\tau =\tau \underset{\sigma k_y}{}[\widehat{c}_{L\sigma k_y}^{}(\overline{l})\widehat{c}_{R\sigma k_y}(l)+\widehat{c}_{R\sigma k_y}^{}(l)\widehat{c}_{L\sigma k_y}(\overline{l})].$$
(37)
In the absence of coupling ($`\tau =0`$), the subgap wave functions of each superconductor are given by Eqs. (30) and (33). Using Eqs. (36), (34), (30), and (33), the tunneling Hamiltonian projected onto the basis of midgap states is

$`𝒫\widehat{H}_\tau =\tau [u_{L0}^{}(\overline{l})u_{R0}(l)+\mathrm{c}.\mathrm{c}.](\widehat{\gamma }_{L0}^{}\widehat{\gamma }_{R0}+\mathrm{H}.\mathrm{c}.)`$
$`=\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}(\varphi /2)(\widehat{\gamma }_{L0}^{}\widehat{\gamma }_{R0}+\widehat{\gamma }_{R0}^{}\widehat{\gamma }_{L0}),`$ (38)
where $`\sqrt{D}=4\tau \mathrm{sin}^2k_Fl/\mathrm{}v_F`$ is the transmission amplitude, and we omitted summation over the diagonal index $`k_y`$. Notice that Eq. (38) is $`4\pi `$-periodic in $`\varphi `$ Kitaev .

Hamiltonian (38) operates between the two degenerate states of the system related by annihilation of the Bogoliubov quasiparticle in the right midgap state and its creation in the left midgap state. In this basis, Hamiltonian (38) can be written as a $`2\times 2`$ matrix

$$𝒫\widehat{H}_\tau =\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}(\varphi /2)\left(\begin{array}{cc}0& 1\\ 1& 0\end{array}\right).$$
(39)
The eigenvectors of Hamiltonian (39) are $`(1,1)`$, i.e. the antisymmetric and symmetric combinations of the right and left midgap states given in Eq. (27). Their eigenenergies are $`E_\pm (\varphi )=\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}(\varphi /2)`$, in agreement with Eq. (18). The tunneling current operator is obtained by differentiating Eqs. (38) or (39) with respect to $`\varphi `$. Because $`\varphi `$ appears only in the prefactor, the operator structures of the current operator and the Hamiltonian are the same, so they are diagonal in the same basis. Thus, the energy eigenstates are simultaneously the eigenstates of the current operator with the eigenvalues

$$I_\pm =\pm \frac{\sqrt{D}e\mathrm{\Delta }_0}{\mathrm{}}\mathrm{sin}\left(\frac{\varphi }{2}\right),$$
(40)
in agreement with Eq. (24). The same basis $`(1,1)`$ diagonalizes Hamiltonian (39) even when a voltage $`V`$ is applied and the phase $`\varphi `$ is time-dependent. Then the initially populated eigenstate with the lower energy produces the current $`I_p=\sqrt{D}(e\mathrm{\Delta }_0/\mathrm{})\mathrm{sin}(eVt/\mathrm{})`$ with the fractional Josephson frequency $`eV/\mathrm{}`$, in agreement with Eq. (24).

### III.5 Josephson current carried by single electrons, rather than Cooper pairs

In the tunneling limit, the transmission coefficient $`D`$ is proportional to the square of the electron tunneling amplitude $`\tau `$: $`D\tau ^2`$. Eqs. (24) and (40) show that the Josephson current in the $`p_x`$-$`p_x`$ junction is proportional to the first power of the electron tunneling amplitude $`\tau `$. This is in contrast to the $`s`$-$`s`$ junction, where the Josephson current (21) is proportional to $`\tau ^2`$. This difference results in the big ratio $`I_p/I_s=2/\sqrt{D}`$ between the critical currents at $`T=0`$ in the $`p_x`$\- and $`s`$-wave cases, as shown in Fig. 2 and discussed in Sec. III.2. The reason for the different powers of $`\tau `$ is the following. In the $`p_x`$-wave case, the transfer of just one electron between the degenerate left and right midgap states is a real (nonvirtual) process. Thus, the eigenenergies are determined from the secular equation (39) already in the first order of $`\tau `$. In the $`s`$-wave case, there are no midgap states, so the transferred electron is taken from below the gap and placed above the gap, at the energy cost $`2\mathrm{\Delta }_0`$. Thus, the transfer of a single electron is a virtual (not real) process. It must be followed by the transfer of another electron, so that the pair of electrons is absorbed into the condensate. This gives the current proportional to $`\tau ^2`$.

This picture implies that the Josephson supercurrent across the interface is carried by single electrons in the $`p_x`$-$`p_x`$ junction and by Cooper pairs in the $`s`$-$`s`$ junction. Because the single-electron charge $`e`$ is a half of the Cooper-pair charge $`2e`$, the frequency of the ac Josephson effect in the $`p_x`$-$`p_x`$ junction is $`eV/\mathrm{}`$, a half of the conventional Josephson frequency $`2eV/\mathrm{}`$ for the $`s`$-$`s`$ junction. These conclusions also apply to a junction between two cuprate $`d`$-wave superconductors in such orientation that both sides of the junction have surface midgap states, e.g. to the $`45^{}/45^{}`$ junction (see Sec. IV.1).

In both the $`p_x`$-$`p_x`$ and $`s`$-$`s`$ junctions, electrons transferred across the interface are taken away into the bulk by the supercurrent of Cooper pairs. In the case of the $`p_x`$-$`p_x`$ junction, a single transferred electron occupies a midgap state until another electron gets transferred. Then the pair of electrons becomes absorbed into the bulk condensate, the midgap state returns to the original configuration, and the cycle repeats. In the case of the $`s`$-$`s`$ junction, two electrons are simultaneously transferred across the interface and become absorbed into the condensate. Clearly, electric charge is transferred across the interface by single electrons at the rate proportional to $`\tau `$ in the first case and by Cooper pairs at the rate proportional to $`\tau ^2`$ in the second case, but the bulk supercurrent is carried by the Cooper pairs in both cases.

### III.6 Josephson effect between triplet superconductors with nonparallel $`𝒏`$-vectors

In this section, we consider the Josephson effect between two $`p_x`$-wave superconductors with nonparallel spin-polarization vectors $`𝒏`$ forming an angle $`\theta `$. This problem was studied in Ref. Vaccarella  using a tunneling Hamiltonian approach. Here we analyze the problem using the BdG formulation. There are experimental indications that the spin-polarization vector $`𝒏`$ is parallel to the crystal axis $`𝒄`$ in the $`(\mathrm{TMTSF})_2\mathrm{X}`$ compounds Chaikin ; Lebed . Then the considered junction can be realized in the geometry shown in Fig. 1(a) where the $`𝒄`$ axes of the two superconductors are rotated relative to each other by the angle $`\theta `$ around the common $`𝒂`$ axis along the chains.

Let us select the spin quantization axis $`z`$ perpendicular to both vectors $`𝒏`$, and the $`x`$ axis in the spin space parallel to the vector $`𝒏`$ of the left superconductor. Then the vector $`𝒏`$ of the right superconductor lies in the $`(x,y)`$ plane at the angle $`\theta `$ to the $`x`$ axes: $`𝒏=(\mathrm{cos}\theta ,\mathrm{sin}\theta ,0)`$. In this representation, the superconducting pairing takes place between electrons with parallel spins:

$`\widehat{c}_\sigma (𝒌)\widehat{c}_\sigma ^{}(𝒌)`$ $``$ $`i\widehat{\sigma }^{(y)}(\widehat{\sigma }^{(x)}n_x+\widehat{\sigma }^{(y)}n_y)\mathrm{\Delta }(𝒌)`$ (43)
$`=`$ $`\left(\begin{array}{cc}e^{i\theta }& 0\\ 0& e^{i\theta }\end{array}\right)\mathrm{\Delta }(𝒌).`$
Then, the Josephson effect can be considered separately for the spin up and down sectors having the phase differences $`\varphi \pm \theta `$, correspondingly. Using Eq. (18) for the $`p_x`$-$`p_x`$ junction, we find the energies of the Andreev bound states for each spin sector

$`E_{a,}`$ $`=`$ $`a\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}\left({\displaystyle \frac{\varphi +\theta }{2}}\right),`$ (44)
$`E_{a,}`$ $`=`$ $`a\mathrm{\Delta }_0\sqrt{D}\mathrm{cos}\left({\displaystyle \frac{\varphi \theta }{2}}\right).`$ (45)
The total Josephson current is obtained by adding the currents carried by the two spin sectors double . For simplicity, below we consider only the case of zero temperature. In the dynamical limit, assuming that the states (44) and (45) with $`a=+`$ are occupied initially and the occupation numbers are preserved dynamically and using Eq. (24), we find a $`4\pi `$-periodic current:

$`I(t)`$ $`=`$ $`{\displaystyle \frac{\sqrt{D}e\mathrm{\Delta }_0}{2\mathrm{}}}\left[\mathrm{sin}\left({\displaystyle \frac{\varphi +\theta }{2}}\right)+\mathrm{sin}\left({\displaystyle \frac{\varphi \theta }{2}}\right)\right]`$ (46)
$`=`$ $`{\displaystyle \frac{\sqrt{D}e\mathrm{\Delta }_0}{\mathrm{}}}\mathrm{sin}\left({\displaystyle \frac{\varphi (t)}{2}}\right)\mathrm{cos}\left({\displaystyle \frac{\theta }{2}}\right).`$
In the static thermodynamic limit, using Eq. (23) at $`T=0`$, we find the dc Josephson current:

$`I`$ $`=`$ $`{\displaystyle \frac{\sqrt{D}e\mathrm{\Delta }_0}{2\mathrm{}}}\{\mathrm{sin}\left({\displaystyle \frac{\varphi +\theta }{2}}\right)\mathrm{sgn}\left[\mathrm{cos}\left({\displaystyle \frac{\varphi +\theta }{2}}\right)\right]`$ (47)
$`+\mathrm{sin}\left({\displaystyle \frac{\varphi \theta }{2}}\right)\mathrm{sgn}\left[\mathrm{cos}\left({\displaystyle \frac{\varphi \theta }{2}}\right)\right]\}.`$
For completeness, let us also consider the Josephson effect between two $`p_y`$-wave or two $`p_z`$-wave superconductors, where the $`y`$ and $`z`$ axes are parallel to the junction plane. In these junctions, midgap states are absent in the $`D0`$ limit, thus the current-phase relation is conventional $`I=I_c\mathrm{sin}\varphi `$. For nonparallel vectors $`𝒏`$, the total Josephson current is the sum of the spin up and down sectors:

$`I`$ $`=`$ $`{\displaystyle \frac{I_c}{2}}[\mathrm{sin}(\varphi +\theta )+\mathrm{sin}(\varphi \theta )]`$ (48)
$`=`$ $`I_c\mathrm{cos}\theta \mathrm{sin}\varphi =I_c(𝒏_L𝒏_R)\mathrm{sin}\varphi .`$
Eq. (48) is consistent with Ref. Vaccarella . In the case where the two vectors $`𝒏`$ are perpendicular ($`\theta =\pi /2`$), the Josephson current (48) for the superconductors without midgap states vanishes, but, according to Eqs. (46) and (47), it is not zero if the midgap states are present.

### III.7 $`𝒔`$-$`𝒑_𝒙`$ junction between singlet and triplet superconductors

In this section, we consider a junction between a singlet $`s`$-wave and a triplet $`p_x`$-wave superconductors. The junction geometry is the same as in Fig. 1(a), where one of the superconductors is taken to be a conventional $`s`$-wave superconductor and another one a Q1D triplet $`p_x`$-wave superconductor, such as $`(\mathrm{TMTSF})_2\mathrm{X}`$.

We choose the spin quantization axis $`z`$ along the polarization vector $`𝒏`$ of the triplet superconductor, so the spin projection $`\sigma `$ on the $`z`$ axis is a good quantum number. In both triplet and singlet superconductors, the Cooper pairing takes place between electrons with opposite spins. However, the pairing potential has the same sign for $`\sigma `$ and $`\overline{\sigma }`$ in the triplet superconductor and the opposite signs in the singlet superconductor. Thus, the phase difference across the Josephson junction is $`\varphi `$ for quasiparticles with $`\sigma =`$ and $`\varphi +\pi `$ for $`\sigma =`$. The energies of the Andreev bound states can be found for each $`\sigma `$ from Eq. (16) together with Eq. (11), where we should use the upper line of Eq. (14) for the left superconductor and the lower line for the right superconductor. To simplify calculations, we consider the case where the magnitudes of the gaps are equal for the $`s`$\- and $`p_x`$-wave superconductors: $`|\mathrm{\Delta }_L|=|\mathrm{\Delta }_R|=\mathrm{\Delta }_0`$. The energies of the Andreev bound states are

$$E_{a,\sigma }=\sigma \mathrm{sgn}(\mathrm{sin}\varphi )\mathrm{\Delta }_0\sqrt{\frac{1+a\sqrt{1D^2\mathrm{sin}^2\varphi }}{2}}.$$
(49)
For each value of the spin index $`\sigma =\pm `$, Eq. (49) gives two Andreev states labeled by the index $`a=\pm `$. In the tunneling limit $`D1`$, we have

$`E_{+,\sigma }`$ $``$ $`\sigma \mathrm{sgn}(\mathrm{sin}\varphi )\mathrm{\Delta }_0\left(1{\displaystyle \frac{1}{8}}D^2\mathrm{sin}^2\varphi \right),`$ (50)
$`E_{,\sigma }`$ $``$ $`{\displaystyle \frac{1}{2}}\sigma \mathrm{\Delta }_0D\mathrm{sin}\varphi .`$ (51)
The energies (49) are plotted in Fig. 3(a) vs. $`\varphi `$ by the solid lines for $`\sigma =`$ and by the dashed lines for $`\sigma =`$. We observe that the branches (50) with $`a=+`$ touch the gap boundaries $`\pm \mathrm{\Delta }_0`$ at $`\varphi =0`$ and $`\pi `$, whereas the branches (51) with $`a=`$ stay in the center of the gap.

In the limit $`D1`$, the central branches with $`a=`$ dominate the energy dependence on $`\varphi `$, and energy minima are achieved at $`\varphi =\pi /2`$ or $`3\pi /2`$. Notice that if the system selects the energy minimum at $`\varphi =\pi /2`$, then the spin down states, shown by the dashed lines in Fig. 3(a), are populated, and the spin up states are empty, so the junction accumulates the spin $`\mathrm{}/2`$ per conducting channel double . If the system selects the energy minimum at $`\varphi =3\pi /2`$, then the junction accumulates the spin $`\mathrm{}/2`$ per conducting channel.

In the limit $`D1`$, we can neglect the energies (50) and obtain the Josephson current by differentiating the energies (51) with respect to $`\varphi `$ using Eq. (19) double . In the dynamical limit, the occupation numbers of the Andreev states (51) are preserved, and the Josephson current has the $`2\pi `$-periodicity, as shown in Fig. 3(c):

$$I(t)\frac{e}{2\mathrm{}}\mathrm{\Delta }_0D\mathrm{cos}\varphi (t).$$
(52)
In the static thermodynamic limit, the system occupies the branch of the minimal energy for each $`\varphi `$, and the Josephson current is $`\pi `$-periodic, as shown in Fig. 3(b):

$$I(\varphi )\frac{e}{2\mathrm{}}\mathrm{\Delta }_0D\mathrm{sgn}(\mathrm{sin}\varphi )\mathrm{cos}\varphi .$$
(53)
The thermodynamic assumption implies that the spin accumulation at the $`s`$-$`p_x`$ junction changes sign when the phase $`\varphi `$ crosses $`\pi `$.

Now let us consider the circuit shown in Fig. 4, where a $`p_x`$-wave superconductor has Josephson junctions at both ends with an $`s`$-wave superconductor closed in a loop. Because the sign of the $`p_x`$-wave pairing potential is opposite for the $`+k_F`$ and $`k_F`$ sheets of the Fermi surface, the two junctions have the relative phase shift $`\pi `$. Naively, one might expect a spontaneous current in this circuit by analogy with the corner SQUID in the cuprates vanHarlingen . However, the system shown in Fig. 4 can accommodate the phase shift $`\pi `$ by selecting the energy minimum at $`\varphi =\pi /2`$ for one junction and the energy minimum at $`\varphi =3\pi /2`$ for another junction. Then, no current circulates in the loop. However, one junction accumulates spins up and another junction spins down, which might be possible to detect experimentally.

The results of the this section clearly show that a Josephson current is possible between singlet and triplet superconductors, in agreement with the earlier findings by Yip Yip . Recently, the Josephson current was calculated for the $`s`$-$`p_x`$ junction in Ref. Asano , but spin accumulation at the junction was not recognized in this paper. The $`s`$-$`p_x`$ junction considered in this section is mathematically equivalent to the $`0^{}/45^{}`$ $`d`$-$`d`$ junction and the $`45^{}`$ junction between an $`s`$-wave and a $`d`$-wave superconductors (see Sec. IV.1). Eq. (49) was obtained for that case in Refs. Riedel ; Barash ; Tanaka2 . However, there is no spin accumulation in junctions between singlet $`s`$\- and $`d`$-wave superconductors, unlike in the $`s`$-$`p_x`$ junction.

## IV Junctions between quasi-two-dimensional superconductors

In this section, we study junctions between quasi-two-dimensional (Q2D) superconductors such as nonchiral $`d`$-wave cuprates and chiral $`p_x\pm ip_y`$-wave ruthenates. For simplicity, we use an isotropic electron energy dispersion law $`\epsilon =\mathrm{}^2(k_x^2+k_y^2)/2m\mu `$ in the $`(x,y)`$ plane. As before, we select the coordinate $`x`$ perpendicular to the junction line and assume that the electron momentum component $`k_y`$ parallel to the junction line is a conserved good quantum number. Then, the 2D problem separates into a set of 1D solutions (10) in the $`x`$ direction labeled by the index $`k_y`$. The Fermi momentum $`k_F`$ and velocity $`v_F`$ are replaced by their $`x`$-components $`k_{Fx}=\sqrt{k_F^2k_y^2}`$ and $`v_{Fx}=\mathrm{}k_{Fx}/m`$. The transmission coefficient of the barrier (9) becomes $`k_y`$-dependent

$$Z(k_y)=Z_0\frac{k_F}{\sqrt{k_F^2k_y^2}},D(k_y)=\frac{4}{Z^2(k_y)+4},$$
(54)
where $`Z_0=\sqrt{2mU_0}/\mathrm{}k_F`$. The total Josephson current is given by a sum over all occupied subgap states labeled by $`k_y`$.

### IV.1 Josephson junctions between $`d`$-wave superconductors

For the cuprates, let us consider a junction parallel to the $`[1,\overline{1}]`$ crystal direction in the $`(𝒂,𝒃)`$ plane and select the $`x`$ axis along the diagonal $`[1,1]`$, as shown in Fig. 5(a). In these coordinates, the $`d`$-wave pairing potential is

$$\widehat{\mathrm{\Delta }}_{\sigma k_y}(x,\widehat{k}_x)=\sigma 2\mathrm{\Delta }_\beta k_y\widehat{k}_x/k_F^2,$$
(55)
where the same notation as in Eq. (6) is used. Direct comparison of Eqs. (55) and (6) demonstrates that the $`d`$-wave superconductor with the $`45^{}`$ junction maps to the $`p_x`$-wave superconductor by the substitution $`\mathrm{\Delta }_0\sigma 2\mathrm{\Delta }_0k_y/k_F`$. Thus, the results obtained in Sec. III for the $`p_x`$-$`p_x`$ junction apply to the $`45^{}/45^{}`$ junction between two $`d`$-wave superconductors with the appropriate integration over $`k_y`$. The energies of the subgap Andreev states are given by Eq. (18) with the $`k_y`$-dependent parameters $`\mathrm{\Delta }_0`$ and $`D`$, and the energies and the wave functions are $`4\pi `$-periodic functions of $`\varphi `$. Thus, the ac Josephson current in the dynamical limit is $`4\pi `$-periodic and has the fractional frequency $`eV/\mathrm{}`$, as in Eqs. (24), (26), and (40). The energies (18) of the subgap states Tanaka1 ; Riedel  and the dc Josephson current (23) in the thermodynamic limit Riedel ; Tanaka2  were calculated for the $`45^{}/45^{}`$ $`d`$-$`d`$ junction before. However, these papers did not recognize the fractional, $`4\pi `$-periodic character of the Josephson effect in the dynamical limit.

On the other hand, if the junction is parallel to the $`[0,1]`$ crystal direction, as shown in Fig. 5(b), then $`\widehat{\mathrm{\Delta }}_{\sigma k_y}(x,\widehat{k}_x)=\sigma \mathrm{\Delta }_\beta (\widehat{k}_x^2k_y^2)/k_F^2`$. This pairing potential is an even function of $`\widehat{k}_x`$, thus it is analogous to the $`s`$-wave pairing potential in Eq. (6). Then, the $`0^{}/0^{}`$ junction between two $`d`$-wave superconductors is analogous to the $`s`$-$`s`$ junction. It should exhibit the conventional $`2\pi `$-periodic Josephson effect with the frequency $`2eV/\mathrm{}`$.

For a generic orientation of the junction line, the $`d`$-wave pairing potential is $`p_x`$-like for some momenta $`k_y`$ and $`s`$-like for other $`k_y`$. Thus, the total Josephson current is a sum of the unconventional and conventional terms:

$$I=C_0\mathrm{sin}(\varphi /2)+C_1\mathrm{sin}(\varphi )+\mathrm{},$$
(56)
where $`C_0`$ and $`C_1`$ are some coefficients. We expect that both terms in Eq. (56) are present for any real junction between $`d`$-wave superconductors because of imperfections in junction orientation. However, the ratio $`C_0/C_1`$ should be maximal for the junction shown in Fig. 5(a) and minimal for the junction shown in Fig. 5(b). In general, whenever the superconductors on both sides of the junction have surface midgap states, we expect to observe the $`4\pi `$-periodic fractional ac Josephson effect. In principle, the effect may be spoiled by the gapless quasiparticles that exist near the gap nodes in a $`d`$-wave superconductor. However, they would affect only a small portion of the Fermi surface near the nodes, and the $`4\pi `$-periodic Josephson effect should survive on the other parts of the Fermi surface, where the gap is big.

The $`45^{}/45^{}`$ junction shown in Fig. 5(a) should not be confused with the $`0^{}/45^{}`$ $`d`$-$`d`$ junction Wendin-ac  or the $`45^{}`$ $`s`$-$`d`$ junction Tanaka-sd ; Zagoskin-sd , much discussed in literature. None of the papers Tanaka-sd ; Zagoskin-sd ; Wendin-ac  treated the problem correctly, because they did not take into account the Andreev bound states in the junction properly. The correct energy spectrum of the Andreev bound states was obtained in Refs. Tanaka1 ; Riedel ; Barash . In the $`0^{}/45^{}`$ $`d`$-$`d`$ and $`45^{}`$ $`s`$-$`d`$ junctions, only one superconductor has midgap states, thus these junctions are mathematically analogous to the $`s`$-$`p_x`$ junction considered in Sec. III.7. The spectrum of the Andreev bound states is given by Eq. (49) without the factor $`\sigma `$, because both superconductors are singlet. The energy levels are plotted vs. $`\varphi `$ in Fig. 3(a), where the solid and dashed lines represent not spin, but positive and negative momenta $`k_y`$. The junction has two energy minima at $`\varphi =\pi /2`$ or $`3\pi /2`$, where the states with only negative or positive momenta $`k_y`$ are filled, thus there are persistent currents along the junction line Huck ; Amin . (On the other hand, there is no spin accumulation, unlike in the $`s`$-$`p_x`$ junction discussed in Sec. III.7.) In the thermodynamic limit, the current-phase relation shown in Fig. 3(b) is $`\pi `$-periodic; however, it requires reversing the currents along the junction line when $`\varphi `$ passes through 0 or $`\pi `$. In the dynamical limit, the current-phase relation shown in Fig. 3(c) is $`2\pi `$-periodic. The first two harmonics $`I=C_1\mathrm{sin}(\varphi )+C_2\mathrm{sin}(2\varphi )`$ have been recently observed experimentally in the $`0^{}/45^{}`$ $`d`$-$`d`$ junction Lindstrom .

### IV.2 Josephson junctions with chiral superconductors

In this section, we study junctions between the chiral $`p_x\pm ip_y`$-wave superconductors $`\mathrm{Sr}_2\mathrm{RuO}_4`$, where the pairing potential is assumed to be $`\mathrm{\Delta }(𝐤)=\mathrm{\Delta }_0(k_x\pm ik_y)/k_F`$ Maeno , and the two signs correspond to opposite chiralities. We assume a uniform orientation of the spin-polarization vector $`𝒏`$ across the junction. This problem was investigated in Ref. Barash-chiral  using the Eilenberger equation for Green’s functions. It was found that the chiral subgap states at the junctions enhance the low-temperature critical Josephson current in symmetric junctions. Here we use the BdG equation to obtain the spectrum of the Andreev bound states. As before, we assume that the momentum component $`k_y`$ parallel to the junction is conserved. Thus, the problem separates into a set of 1D solutions in the $`x`$ direction perpendicular to the junction plane, and we can use the method of Sec. III.1.

First we consider a junction between two superconductors with opposite chiralities, as illustrated in the first column of Fig. 6(a). In this case, $`\mathrm{\Delta }_L=\mathrm{\Delta }_0(k_x+ik_y)/k_F`$ and $`\mathrm{\Delta }_R=e^{i\varphi }\mathrm{\Delta }_0(k_xik_y)/k_F`$. When the barrier is not transparent ($`D=0`$), each superconductor has chiral Andreev surface states with the same energy dispersion $`E(k_y)=k_y\mathrm{\Delta }_0/k_F`$ Honerkamp98 . The electron tunneling amplitude $`\tau \sqrt{D}`$ produces a matrix element mixing the two states in the first-order degenerate perturbation theory. Thus, the two energy spectra repel with the splitting proportional to $`\sqrt{D}`$. From Eq. (16), we find the following subgap energies:

$$E=\frac{\mathrm{\Delta }_0}{k_F}\left(k_y\sqrt{1D\mathrm{cos}^2\frac{\varphi }{2}}\pm \sqrt{k_F^2k_y^2}\sqrt{D}\mathrm{cos}\frac{\varphi }{2}\right).$$
(57)
The energy levels splitting oscillates with the period $`4\pi `$ as a function of $`\varphi `$: $`\delta E=(\mathrm{\Delta }_0/k_F)\sqrt{k_F^2k_y^2}\sqrt{D}\mathrm{cos}\varphi /2`$. The splitting depends on $`k_y`$ through the square-root prefactor and through the dependence of $`D`$ on $`k_y`$ in Eq. (54), and vanishes at $`k_y=\pm k_F`$. The energy dispersion (57) is plotted vs. $`k_y`$ in the second and third columns of Fig. 6(a) for several values of $`\varphi `$. The spectrum of excitations is gapless because of the chiral dispersion in $`k_y`$. Thus, it is reasonable to assume that the occupation numbers of the subgap states are in instantaneous thermodynamic equilibrium for any phase $`\varphi `$. Then, the Josephson current is a $`2\pi `$-periodic function of $`\varphi `$, as illustrated at zero temperature in the fourth column of Fig. 6(a), even though the energy levels (57) are $`4\pi `$-periodic functions of $`\varphi `$.

Now let us consider the case of two superconductors with opposite chiralities, as illustrated in the first column of Fig. 6(b). When the two superconductors are disconnected ($`D=0`$), their chiral Andreev surface states have opposite dispersions $`E=\pm k_y\mathrm{\Delta }_0/k_F`$, thus they are nondegenerate. The electron tunneling amplitude $`\tau \sqrt{D}`$ repels the energy levels around the intersection point $`k_y=0`$. From Eq. (16), we find the following subgap energies:

$$E=\pm \frac{\mathrm{\Delta }_0}{k_F}\sqrt{(1D)k_y^2+Dk_F^2\mathrm{cos}^2\frac{\varphi }{2}}.$$
(58)
The energy dispersion (58) is plotted vs. $`k_y`$ in the second and third columns of Fig. 6(b) for several values of $`\varphi `$. The energy splitting around $`k_y=0`$ is a $`2\pi `$-periodic function of $`\varphi `$ and vanishes at $`\varphi =\pi `$. The Josephson current is a $`2\pi `$-periodic function of $`\varphi `$, as illustrated at zero temperature in the fourth column of Fig. 6(b).

Now let us consider a junction between an $`s`$-wave and a $`p_x+ip_y`$-wave superconductors shown in the first column of Fig. 6(c). The Josephson current was calculated in this case in Ref. Asano  using the method of Green’s functions. However, the energies of the Andreev bound states were not written explicitly. The subgap states in this junction are obtained by solving Eq. (16) in the manner similar to the 1D $`s`$-$`p_x`$ junction. For simplicity, we assume that the magnitudes of the pairing potentials in both superconductors are the same: $`|\mathrm{\Delta }_L|=|\mathrm{\Delta }_R|=\mathrm{\Delta }_0`$. The square of the subgap energies is given by the following expression

$`E_{a,\sigma }^2`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Delta }_0^2}{2}}(1+R\stackrel{~}{k}_y^2\sigma D\stackrel{~}{k}_y\mathrm{sin}\varphi `$
$`+a\sqrt{1\stackrel{~}{k}_y^2}\sqrt{1(R\stackrel{~}{k}_y\sigma D\mathrm{sin}\varphi )^2}),`$
where $`R=1D`$ is the reflection coefficient, and $`\stackrel{~}{k}_y=k_y/k_F`$. The signs of the energies are

$`\mathrm{sgn}E_{a,\sigma }`$ $`=`$ $`\mathrm{sgn}(R\stackrel{~}{k}_y+\sigma D\mathrm{sin}\varphi `$
$`+a\stackrel{~}{k}_y\sqrt{{\displaystyle \frac{1(R\stackrel{~}{k}_y\sigma D\mathrm{sin}\varphi )^2}{1\stackrel{~}{k}_y^2}}}).`$
For a given $`\sigma `$, there are two branches of energies labeled by the index $`a=\pm `$. The energy dispersions $`E_{\pm ,}(k_y)`$ are shown in the second and third columns of Fig. 6(c) for several phases $`\varphi `$. In the limit of impenetrable barrier $`D0`$, the energy branch with $`a=+`$ approaches to the gap edges $`|E_+|\mathrm{\Delta }_0`$, whereas the branch with $`a=`$ approaches to the energy dispersion $`E_{}k_y\mathrm{\Delta }_0/k_F`$ of the chiral surface states in the $`p_x+ip_y`$-wave superconductor Honerkamp98 .

The energy $`E_{a,\sigma }(k_y)`$ for a given $`\sigma `$ is a $`2\pi `$-periodic function of $`\varphi `$. The energy $`E_{a,\overline{\sigma }}(k_y)`$ is obtained from $`E_{a,\sigma }(k_y)`$ by the shift $`\varphi \varphi +\pi `$, as discussed in Sec. III.7. Thus, the Josephson current (20) in the static thermodynamic limit, obtained by summation over $`\sigma `$ and $`k_y`$, is a $`\pi `$-periodic function of $`\varphi `$, as shown in the fourth column of Fig. 6(c), in agreement with Ref. Asano . Similarly to the $`s`$-$`p_x`$ junction considered in Sec. III.7, the $`s`$-($`p_x+ip_y`$) junction has two equal energy minima Asano  at $`\varphi =\pi /2`$ and $`3\pi /2`$ accompanied by accumulation of the down spin for $`\varphi =\pi /2`$ and the up spin for $`\varphi =3\pi /2`$.

## V Experimental observation of the fractional ac Josephson effect

Conceptually, the setup for experimental observation of the fractional ac Josephson effect is straightforward. One should apply a dc voltage $`V`$ to the junction and measure frequency spectrum of microwave radiation from the junction, expecting to detect a peak at the fractional frequency $`eV/\mathrm{}`$. Higher harmonics, such as $`2eV/\mathrm{}`$, may also be present because of Eq. (56) and circuit nonlinearities, but an observation of the 1/2 subharmonic of the conventional Josephson frequency $`2eV/\mathrm{}`$ would be the signature of the effect.

Josephson radiation at the conventional frequency $`2eV/\mathrm{}`$ was first observed experimentally almost 40 years ago in Kharkov Yanson1 ; Yanson2 , followed by further work Langenberg ; Yanson3 . In Ref. Yanson2 , the spectrum of microwave radiation from tin junctions was measured, and a sharp peak at the frequency $`2eV/\mathrm{}`$ was found. Without any attempt to match impedances of the junction and waveguide, Dmitrenko and Yanson Yanson2  found the signal several hundred times stronger than the noise and the ratio of linewidth to the Josephson frequency less than $`10^3`$. More recently, a peak of Josephson radiation was observed in Ref. Lukens  in indium junctions at the frequency 9 GHz with the width 36 MHz. In Ref. Mulller , a peak of Josephson radiation was observed around 11 GHz with the width 50 MHz in $`\mathrm{Bi}_2\mathrm{Sr}_2\mathrm{CaCu}_2\mathrm{O}_8`$ single crystals with the current along the $`𝒄`$ axis perpendicular to the layers.

To observe the fractional ac Josephson effect predicted in this paper, it is necessary to perform the same experiment with the $`45^{}/45^{}`$ cuprate junctions shown in Fig. 5(a). For control purposes, it is also desirable to measure frequency spectrum for the $`0^{}/0^{}`$ junction shown in Fig. 5(b), where a peak at the frequency $`eV/\mathrm{}`$ should be minimal. It should be absent completely in a conventional $`s`$-$`s`$ junction, unless the junction enters a chaotic regime with period doubling Miracky ; Lobb . The high-$`T_c`$ junctions of the required geometry can be manufactured using the step-edge technique. Bicrystal junctions are not appropriate, because the crystal axes $`𝒂`$ and $`𝒃`$ of the two superconductors are rotated relative to each other in such junctions. As shown in Fig. 5(a), we need the junction where the crystal axes of the two superconductors have the same orientation. Unfortunately, attempts to manufacture Josephson junctions from the Q1D organic superconductors $`(\mathrm{TMTSF})_2\mathrm{X}`$ failed thus far.

The most common way of studying the ac Josephson effect is observation of the Shapiro steps Shapiro . In this setup, the Josephson junction is irradiated by microwaves with the frequency $`\omega `$, and steps in dc current are detected at the dc voltages $`V_n=n\mathrm{}\omega /2e`$. Unfortunately, this method is not very useful to study the effect that we predict. Indeed, our results are effectively obtained by the substitution $`2ee`$. Thus, we expect to see the Shapiro steps at the voltages $`V_m=m\mathrm{}\omega /e=2m\mathrm{}\omega /2e`$, i.e. we expect to see only *even* Shapiro steps. However, when both terms are present in Eq. (56), they produce both even and odd Shapiro steps, so it would be difficult to differentiate the novel effect from the conventional Shapiro effect. Notice also that the so-called fractional Shapiro steps observed at the voltage $`V_{1/2}=\mathrm{}\omega /4e`$ corresponding to $`n=1/2`$ have nothing to do with the effect that we propose. They originate from the higher harmonics in the current-phase relation $`I\mathrm{sin}(2\varphi )`$. The fractional Shapiro steps have been observed in cuprates Early ; Horng ; Borisenko , but also in conventional $`s`$-wave superconductors Clarke . Another method of measuring the current-phase relation in cuprates was employed in Ref. ZK , but connection with our theoretical results is not clear at the moment.

## VI Conclusions

In this paper, we study suitably oriented $`p_x`$-$`p_x`$ or $`d`$-$`d`$ Josephson junctions, where the superconductors on both sides of the junction originally have the surface Andreev midgap states. In such junctions, the Josephson current $`I`$, carried by the hybridized subgap Andreev bound states, is a $`4\pi `$-periodic function of the phase difference $`\varphi `$: $`I\mathrm{sin}(\varphi /2)`$, in agreement with Ref. Kitaev . Thus, the ac Josephson current should exhibit the fractional frequency $`eV/\mathrm{}`$, a half of the conventional Josephson frequency $`2eV/\mathrm{}`$. In the tunneling limit, the Josephson current is proportional to the first power of the electron tunneling amplitude, not the square as in the conventional case Tanaka2 ; Riedel ; Barash . Thus, the Josephson current in the considered case is carried across the interface by single electrons with charge $`e`$, rather than by Copper pairs with charge $`2e`$. The fractional ac Josephson effect can be observed experimentally by measuring frequency spectrum of microwave radiation from the junction and detecting a peak at $`eV/\mathrm{}`$.

In $`p_x`$-$`p_x`$ junctions with nonparallel orientation of the spin-polarization vectors $`𝒏`$, the Josephson current depends on the relative angle between the vectors $`𝒏`$ Vaccarella . The Josephson current is permitted between singlet and triplet superconductors, but, in the static thermodynamic limit, the current-phase relation is $`\pi `$-periodic Yip . The $`s`$-$`p`$ junction has two equal minima in energy at $`\varphi =\pi /2`$ and $`3\pi /2`$ Asano , characterized by accumulation of the up or down spins (oriented relative to the vector $`𝒏`$) in the junction. In Josephson junctions between chiral $`p_x\pm ip_y`$-wave superconductors, the Andreev bound states are also chiral. In the static thermodynamic limit, the current-phase relation has the period of $`2\pi `$ in the chiral $`p`$-$`p`$ junctions Barash-chiral  and the period of $`\pi `$ in the chiral $`s`$-$`p`$ junctions Asano .

###### Acknowledgements.

VMY and HJK thank F. C. Wellstood, C. J. Lobb, and A. Yu. Kitaev for useful discussions. KS thanks S. M. Girvin for support. The work was supported by the NSF Grant DMR-0137726.

*Note added in proof.* The fractional Josephson effect discussed in our paper is similar to the fractional quantum Hall effect Thouless . Both involve existence of several equivalent ground states, whose energy levels cross: Compare Fig. 1c of our paper and Fig. 2a of Ref. Thouless .