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# Untitled Document

Relativistically extended Blanchard recurrence relation for hydrogenic matrix elements

R. P. Martínez-y-Romero**E-mail: rodolfo@dirac.fciencias.unam.mx

Facultad de Ciencias, Universidad Nacional Autónoma de México,

Apartado Postal 50-542, México City, Distrito Federal C. P. 04510.

H. N. Núñez-Yépez† E-mail: nyhn@xanum.uam.mx

Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa

Apartado Postal 55–534, Iztapalapa, Distrito Federal C. P. 09340 México.

A. L. Salas-Brito ‡ E-mail: asb@correo.azc.uam.mx

Laboratorio de Sistemas Dinámicos, Departamento de Ciencias Básicas,

Universidad Autónoma Metropolitana-Azcapotzalco.

Apartado Postal 21–726, Coyoacán, Distrito Federal C. P. 04000 México.

Abstract.

General recurrence relations for arbitrary non-diagonal, radial hydrogenic matrix elements are derived in Dirac relativistic quantum mechanics. Our approach is based on a generalization of the second hypervirial method previously employed in the non-relativistic Schrödinger case. A relativistic version of the Pasternack-Sternheimer relation is thence obtained in the diagonal (i.e. total angular momentum and parity the same) case, from such relation an expression for the relativistic virial theorem is deduced. To contribute to the utility of the relations, explicit expressions for the radial matrix elements of functions of the form $`r^\lambda `$ and $`\beta r^\lambda `$ —where $`\beta `$ is a Dirac matrix— are presented.

Keywords: Relativistic hydrogen atom, recurrence relations, non-diagonal radial matrix elements, relativistic Pasternack-Sternheimer relation.

PACS: 3.65.Ca

I. Introduction

Recurrence relations for matrix elements are very useful tools in quantum calculations \[1–5\] since the direct computation of such elements is generally very cumbersome. An interesting example is the Blanchard’s relation which is a useful recurrence formula for arbitrary (i.e. not necessarily diagonal) non-relativistic matrix elements of the form $`n_1l_1|r^\lambda |n_2l_2`$, where the $`|nl`$ stand for non-relativistic hydrogenic radial energy eigenstates; according to this relation, once any three successive matrix elements of powers of the radial coordinate, $`r`$, are known, any other can be deduced in terms of the previously known ones. The Blanchard recurrence relation was derived more than twenty five years ago using a calculation-intensive method , which is not surprising since in general recurrence relations are rather difficult to obtain.

Trying to overcome such difficulties, different approaches have been proposed for obtaining general recurrence relations; some of them are based on algebraic methods, others use sum rules and hypervirial theorems \[4,7–10\]. In particular, a hypervirial result has been employed to obtain the Blanchard relation in a more compact way than in the original deduction . In relativistic quantum mechanics, on the other hand, and despite its physical and its possible chemical interest , excepting for the results reported in , there are not as yet general recurrence relations which could be used for calculating matrix elements of powers of the radial coordinate in terms of previously known ones. We should mention though that there are previous efforts in such direction, in which closed forms for certain relativistic matrix elements have been evaluated  and certain, mostly diagonal, recurrence relations for relativistic and quasirelativistic states have been calculated  .

In this paper we employ a relativistic calculation inspired on the hypervirial method  to deduce a recurrence relation for the, in general, non-diagonal radial matrix elements of succesive powers of $`r^\lambda `$ and of $`\beta r^\lambda `$—where $`\beta `$ is a 4$`\times `$4 Dirac matrix \[18–20\]— for relativistic hydrogenic states in the energy basis. The assumptions we use are that the nucleus is point-like and fixed in space, and that a description using the Dirac equation is valid. We first study the recurrence relations in the general case, in which the matrix elements are taken between states with different principal quantum numbers $`n_1n_2,`$, different total angular momentum quantum numbers $`j_1j_2`$, $`m_{j_1}m_{j_2}`$, and, as we use the quantum number $`ϵ(1)^{j+l1/2}`$ instead of parity for labelling the hydrogenic eigenstates, where $`ϵ_1ϵ_2`$. We find that in general the recurrence relations depend on matrix elements of both powers of $`r`$ and of $`\beta r`$. In practical terms this means that we need two recurrence relations as the relativistic version of the single-equation Blanchard relation \[Eqs. (6) and (7) of section II\]. Given its special interest, we study in particular the case where the total angular momentum and parity become equal, $`j_1=j_2`$ and $`ϵ_1=ϵ_2`$, in the two states—not mattering the relative values of the principal quantum number $`n`$. We also address the completely diagonal case where $`n_1=n_2`$, $`j_1=j_2`$, and $`ϵ_1=ϵ_2`$. Both of the particular cases mentioned above require special treatment for avoiding possible divisions by zero in the general expressions; such results are immediately used to obtain a relativistic version of the Pasternack-Sternheimer rule  and to obtain an expression for the relativistic virial theorem .

This paper is organized as follows. In section II we review the second hypervirial scheme used for deriving the non-relativistic Blanchard relation. In section III, after obtaining the radial Hamiltonian useful for implementing the hypervirial result in relativistic quantum mechanics, we proceed to use it to deduce by a long but direct calculation the relativistic recurrence formulae. In section IV we study in particular the diagonal case ($`j_2=j_1`$, $`ϵ_2=ϵ_1`$) to derive the relativistic Pasternak-Sternheimer rule and use it (when $`n_1=n_2`$) to obtain a version of the relativistic virial theorem. In the Appendix, we obtain explicit expressions for diagonal and non-diagonal matrix elements for any power of $`r`$ and of $`\beta r`$ between radial relativistic hydrogenic states. As it becomes evident, such results are rather cumbersome for relatively large values of the power; for small values, on the other hand, they are better regarded as starting values for the recurrence relations derived in section III of this article. Furthermore, these results can be of utility not only for relativistic atomic and molecular studies but also for evaluating matrix elements of interactions designed to test Lorentz and CPT invariance in hydrogen .

II. The non-relativistic recurrence relation

Both the Blanchard relation and its predecesor the Kramers selection rule, were originally obtained employing directly the Schrödinger equation together with appropriate boundary conditions and, at least in the former case, a great deal of computations . A much simpler approach based on a generalized hypervirial result and certain Hamiltonian identities has been developed to simplify the computations leading to the Blanchard relation . This technique seemed to us an appropriate starting point for deriving relativistic recurrence formulae. It is with such relativistic extension in mind that we review in this section the hypervirial method as it is applied in non-relativistic quantum mechanics. In this section, as in most of the paper, we employ atomic units $`\mathrm{}=m=e=1`$.

The idea is to start with the radial Schrödinger equation for a central potential $`V(r)`$ written in the form

$$H_k|n_kl_k=E_{n_kl_k}|n_kl_k,$$
$`(1)`$
where $`|n_kl_k=\psi _{n_kl_k}(r)`$ and $`E_{n_kl_k}`$ are an energy eigenfunction and its corresponding energy eigenvalue with principal and angular momentum quantum numbers, $`n_k`$ and $`l_k`$, respectively; $`k`$ is just a label, and $`H_k`$, the non-relativistic radial Hamiltonian, is given by

$$H_k=\frac{1}{2}\frac{d^2}{dr^2}\frac{1}{r}\frac{d}{dr}+\frac{l_k(l_k+1)}{2r^2}+V(r).$$
$`(2)`$
Although we want to calculate the radial matrix elements of terms of the form $`r^\lambda `$, it is best for our purposes to consider first matrix elements of an arbitrary radial function $`f(r)`$. With such choice we can readily show  that

$$(E_iE_k)n_il_i|f(r)|n_kl_k=n_il_i|\left(\frac{1}{2}f^{^{\prime \prime }}f^{^{}}\frac{d}{dr}\frac{1}{r}f^{^{}}+\frac{\mathrm{\Delta }_{ik}^{}}{2}\frac{f}{r^2}\right)|n_kl_k,$$
$`(3)`$
where we use $`\mathrm{\Delta }_{ik}^{}l_i(l_i+1)l_k(l_k+1)`$, $`E_kE_{n_kl_k}`$, and the primes stand for radial derivatives. Please recall that the matrix element of an arbitrary radial function $`f(r)`$ is

$$n_il_i|f(r)|n_kl_k=_0^{\mathrm{}}r^2\psi _{n_il_i}^{}(r)f(r)\psi _{n_kl_k}(r)𝑑r.$$
$`(4)`$
To establish the result we are after, we apply the previous result (3) to the radial function $`\xi (r)H_if(r)f(r)H_k`$, to find

$$\begin{array}{cc}\hfill 2(E_iE_k)^2n_il_i|& f(r)|n_kl_k=\hfill \\ & n_il_i|(H_i(H_if(r)f(r)H_k)(H_if(r)f(r)H_k)H_k+\hfill \\ & H_i(H_if(r)f(r)H_k)(H_if(r)f(r)H_k)H_k)|n_kl_k.\hfill \end{array}$$
$`(5)`$
This is the generalized second hypervirial valid for arbitrary radial potential energy functions, $`V(r)`$, introduced in Eq. (8) of Ref. 11.

The second hypervirial takes a particularly simple form when $`f(r)`$ is a power of the position, let us say $`f(r)=r^{\lambda +2}`$; using this expression for $`f(r)`$ and restricting ourselves to the Coulomb potential, $`V(r)=Z/r`$, we obtain , after a long —but much shorter than in — direct calculation, the Blanchard relation

$$\begin{array}{cc}\hfill \lambda \left(E_iE_k\right)^2n_il_i|r^{\lambda +2}|n_kl_k& =c_0n_il_i|r^\lambda |n_kl_k+c_1n_il_i|r^{\lambda 1}|n_kl_k\hfill \\ & +c_2n_il_i|r^{\lambda 2}|n_kl_k;\hfill \end{array}$$
$`(6)`$
where the hydrogenic energy eigenvalues are $`E_a=Z^2/2n_a^2`$, independent of $`l`$, and

$$\begin{array}{cc}\hfill c_0& =Z^2(\lambda +1)\left[(l_il_k)(l_i+l_k+1)\left(\frac{1}{n_i^2}\frac{1}{n_k^2}\right)+\lambda (\lambda +2)\left(\frac{1}{n_k^2}+\frac{1}{n_i^2}\right)\right]\hfill \\ \hfill c_1& =2Z\lambda (\lambda +2)(2\lambda +1)\hfill \\ \hfill c_2& =\frac{1}{2}(\lambda +2)\left[\lambda ^2(l_kl_i)^2\right]\left[(l_k+l_i+1)^2\lambda ^2\right].\hfill \end{array}$$
$`(7)`$
From this result we can also obtain, as special cases of the Blanchard recurrence relation (6), first the Pasternack-Sternheimer selection rule :

$$n_il_i|\frac{Z}{r^2}|n_kl_k=0,$$
$`(8)`$
saying that the matrix element of the potential $`1/r^2`$ vanishes between radial states of central potentials when their angular momenta coincide and when the corresponding energy eigenvalues depend on the principal quantum number only. Second, in the completely diagonal case (i.e. $`n_i=n_k`$, $`l_i=l_k`$), we can further obtain the non-relativistic quantum virial theorem

$$V=Z\frac{1}{r}=2E.$$
$`(9)`$
As we exhibit in section IV, we can obtain analogous results using our recurrence relations in relativistic quantum mechanics.

III. The relativistic recurrence relations.

In this section we apply the method sketched in section II to the relativistic Dirac case. We clearly need to start with a radial Dirac Hamiltonian analogous to (2). To obtain such Hamiltonian we start with the Dirac Hamiltonian $`H_D`$ and the corresponding time-independent Dirac equation for a central potential

$$H_D=c\alpha \alpha \alpha \text{p}+\beta c^2+V(r),H_D\mathrm{\Psi }(𝐫)=E\mathrm{\Psi }(𝐫);$$
$`(10)`$
where we are using atomic units, $`\alpha `$$`\alpha `$$`\alpha `$ and $`\beta `$ are the 4$`\times `$4 Dirac matrices \[18–20\], which in the Dirac representation are given by

$$\alpha \alpha \alpha =\left(\begin{array}{cc}0& \sigma \sigma \sigma \\ \sigma \sigma \sigma & 0\end{array}\right),\beta =\left(\begin{array}{cc}1& 0\\ 0& 1\end{array}\right),$$
$`(11)`$
where the 1’s and 0’s stand respectively, for $`2\times 2`$ unit and zero matrices and the $`\sigma `$$`\sigma `$$`\sigma `$ is the vector composed by the three $`2\times 2`$ Pauli matrices $`\sigma \sigma \sigma =(\sigma _x,\sigma _y,\sigma _z)`$. Please notice that, despite the selection of natural units we shall, where it aids interpretation, reinsert the appropriate dimensional factors in certain equations. The energy eigenvalues are given explicitly in Eq. (63) of section V. The Hamiltonian $`H_D`$ is rotationally invariant, hence the solutions of the Dirac equation (10) can be written in the alternative but entirely equivalent forms

$$\mathrm{\Psi }(r,\theta ,\varphi )=\frac{1}{r}\left(\begin{array}{c}F_{njϵ}(r)𝒴_{jm_z}(\theta ,\varphi )\\ \\ iG_{njϵ}(r)𝒴_{jm_z}^{}(\theta ,\varphi )\end{array}\right)=\frac{1}{r}\left(\begin{array}{c}F_{n\kappa }(r)\chi _{\kappa m_z}(\theta ,\varphi )\\ \\ iG_{n\kappa }(r)\chi _{\kappa m_z}(\theta ,\varphi )\end{array}\right),$$
$`(12)`$
where $`\chi _{\kappa m_z}`$ and $`\chi _{\kappa m_z}`$, or $`𝒴_{jm}`$ and $`𝒴_{jm}^{}`$, are spinor spherical harmonics of opposite parity, and $`\kappa =ϵ(j+1/2)`$ is the eigenvalue of the operator $`\mathrm{\Lambda }\beta (1+\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }𝐋)`$ which commutes with $`H_D`$ (where $`\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }\sigma \sigma \sigma I=\text{diag}(\sigma \sigma \sigma ,\sigma \sigma \sigma )`$). The second form in (12) is the preferred in Ref. 18. Parity is a good quantum number in the problem because central potentials are invariant under reflections; parity varies as $`(1)^l`$ and, according to the triangle’s rule of addition of momenta, the orbital angular momentum is given by $`l=j\pm 1/2`$. But, instead of working directly with parity or with $`\kappa `$, we prefer the quantum numbers $`j`$ and $`ϵ`$, introduced above, which can be shown also to be

$$ϵ=\{\begin{array}{cc}1\hfill & \text{If }l=j+\frac{1}{2},\hfill \\ & \\ 1\hfill & \text{If }l=j\frac{1}{2}\text{,}\hfill \end{array}$$
$`(13)`$
thus $`l=j+ϵ/2`$ in all cases. We also define $`l^{}=jϵ/2`$; accordingly, the spherical spinor $`𝒴_{jm}`$ depends on $`l`$ whereas the spherical spinor $`𝒴_{jm}^{}`$, which has the opposite parity, depends on $`l^{}`$. Writing the solutions in the form (12) completely solves the angular part of the problem.

To construct the radial Hamiltonian, we use the relation

$$(\alpha \alpha \alpha 𝐫)(\alpha \alpha \alpha 𝐩)=(\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }𝐫)(\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }𝐩)=𝐫𝐩+i\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }𝐋;$$
$`(14)`$
we then use $`𝐉^2=\left[𝐋+(1/2)\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }\right]^2=𝐋^2+\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }𝐋+3/4`$ but for expressing the term $`𝐋\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }`$, we also need an expression for $`𝐋^2`$ acting on the eigenfunctions (12). Directly from this equation we see that when $`𝐋^2`$ is applied to any central potential state, the big component of the state function behaves with the orbital quantum number $`l=j+ϵ/2`$, whereas the small one does so with the orbital quantum number $`l^{}=jϵ/2`$; we have then,

$$l(l+1)=j(j+1)+ϵ(j+\frac{1}{2})+\frac{1}{4},$$
$`(15)`$
for the big component, and

$$l^{}(l^{}+1)=j(j+1)ϵ(j+\frac{1}{2})+\frac{1}{4},$$
$`(16)`$
for the small one. The action of $`𝐋^2`$ upon a solution of the form (12) is therefore always of the form

$$𝐋^2=j(j+1)+\beta ϵ(j+\frac{1}{2})+\frac{1}{4},$$
$`(17)`$
where $`\beta `$ is the Dirac matrix (11). From this result we obtain the term $`𝐋\mathrm{\Sigma }\mathrm{\Sigma }\mathrm{\Sigma }`$ and, substituting it into $`(\alpha \alpha \alpha 𝐩)`$, we finally obtain

$$(\alpha \alpha \alpha 𝐩)=\alpha _r[p_ri\beta \frac{ϵ}{r}(j+\frac{1}{2})],$$
$`(18)`$
where

$$\alpha _r\frac{1}{r}\alpha \alpha \alpha 𝐫,p_r=\frac{i}{r}\left(1+r\frac{d}{dr}\right).$$
$`(19)`$
We are now ready to write the relativistic radial Hamiltonian, and the corresponding radial Dirac equation, as

$$\begin{array}{cc}& H_k=c\alpha _r\left[p_ri\beta \frac{ϵ_k}{r}\left(j_k+\frac{1}{2}\right)\right]+\beta c^2+V(r),\hfill \\ & H_k\psi _k(r)=E_k\psi _k(r),\hfill \end{array}$$
$`(20)`$
where we introduced the purely radial eigenfunctions

$$\psi _k(r)\frac{1}{r}\left(\begin{array}{c}F_{n_kj_kϵ_k}(r)\\ iG_{n_kj_kϵ_k}(r)\end{array}\right)$$
$`(21)`$
in a $`2\times 2`$ representation where, $`\beta =`$ diag$`(+1,1)`$, $`\alpha _r=\left(\begin{array}{cc}0& 1\\ 1& 0\end{array}\right)`$, and the radial Dirac equation becomes then

$$\left[\begin{array}{cc}c^2+\left(V_k(r)E_k\right)& c\left(ϵ_k\left(j_k+1/2\right)/r+d/dr\right)\\ \\ c\left(ϵ_k\left(j_k+1/2\right)/r+d/dr\right)& c^2+\left(V_k(r)E_k\right)\end{array}\right]\left[\begin{array}{c}F_{n_kj_kϵ_k}(r)\\ \\ G_{n_kj_kϵ_k}(r)\end{array}\right]=0.$$
$`(22)`$
Though this explicit representation can be used for our problem , it is not really necessary since all our results are representation independent.

The relativistic recurrence relation we are after, can be deduced using a similar reasoning as the used in section II for the non-relativistic case. Let us first calculate the non-diagonal matrix element of an arbitrary radial function $`f(r)`$

$$\begin{array}{cc}\hfill (E_2E_1)n_2j_2ϵ_2|f(r)|n_1& j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|H_2f(r)f(r)H_1|n_1j_1ϵ_1\hfill \\ & =icn_2j_2ϵ_2|\alpha _r\left(f^{}(r)+\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)|n_1j_1ϵ_1,\hfill \end{array}$$
$`(23)`$
where from now on the labelling in the kets stand for the three quantum numbers $`n_k`$, $`j_k`$, and $`ϵ_k`$, we have defined $`\mathrm{\Delta }_{21}^{}ϵ_2(2j_2+1)ϵ_1(2j_1+1)`$, and the matrix elements of radial functions are calculated as

$$\begin{array}{cc}\hfill n_2j_2ϵ_2|f(r)|n_1j_1ϵ_1& =f(r)\left(F_2^{}(r)F_1(r)+G_2^{}(r)G_1(r)\right)𝑑r,\hfill \\ \hfill n_2j_2ϵ_2|\beta f(r)|n_1j_1ϵ_1& =f(r)\left(F_2^{}(r)F_1(r)G_2^{}(r)G_1(r)\right)𝑑r.\hfill \end{array}$$
$`(24)`$
where the subscripts stand for the 3 quantum numbers specifying the state.

We next proceed to calculate a “second order iteration” by substituting $`f(r)\xi (r)=H_2f(r)f(r)H_1`$ in the last expression. Let us calculate first $`H_2\xi `$ and $`\xi H_1`$,

$$\begin{array}{cc}& H_2\xi =c^2\left(\frac{f^{}(r)}{r}+f^{\prime \prime }(r)+f^{}(r)\frac{d}{dr}\right)c^2\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta \left(f^{}(r)+f(r)\frac{d}{dr}\right)+\hfill \\ & c^2\frac{ϵ_2\left(2j_2+1\right)}{2r}\beta \left(f^{}(r)+\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)ic\alpha _r\left(f^{}(r)+\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)\left(V(r)\beta c^2\right),\hfill \end{array}$$
$`(25)`$
and

$$\begin{array}{cc}& \xi H_1=\frac{c^2}{r}\left(f^{}(r)\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)c^2\left(f^{}(r)\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)\frac{d}{dr}+\hfill \\ & c^2\frac{ϵ_1\left(2j_1+1\right)}{2r}\beta \left(f^{}(r)\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)ic\alpha _r\left(f^{}(r)+\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)\left(V(r)+\beta c^2\right).\hfill \end{array}$$
$`(26)`$
Then, we write down the difference of the matrix elements associated with Eqs. (25) and (26)

$$\begin{array}{cc}& (E_2E_1)^2n_2j_2ϵ_2|f(r)|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c^2\frac{\mathrm{\Delta }_{21}^{}}{2r^2}\beta f(r)c^2f^{\prime \prime }(r)c^2\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f^{}(r)c^2\frac{\mathrm{\Delta }_{21}^{}}{r}\beta f(r)\frac{d}{dr}+\hfill \\ & c^2\frac{\mathrm{\Delta }_{21}^+}{2r}\beta f^{}(r)+c^2\left(\frac{\mathrm{\Delta }_{21}^{}}{2r}\right)^2f(r)+2ic^3\alpha _r\beta \left(f^{}(r)+\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)\right)|n_1j_1ϵ_1.\hfill \end{array}$$
$`(27)`$
where we have defined $`\mathrm{\Delta }_{21}^+ϵ_2(2j_2+1)+ϵ_1(2j_1+1)`$. Please notice that here and in what follows we are always assuming $`\mathrm{\Delta }_{21}^{}0`$.

This last expression (27) is the direct relativistic equivalent of the generalized second hypervirial \[Cf. Eq. (5) above\]. The expression involves the operator $`d/dr`$, but here, due to the presence of Dirac matrices in the result, we cannot use the trick employed in the non relativistic case where we took advantage of the Hamiltonian to simplify the calculation . Instead, let us calculate the following second order iteration for non-diagonal matrix elements

$$\begin{array}{cc}\hfill n_2j_2ϵ_2|H_2\xi & +\xi H_1|n_1j_1ϵ_1=(E_2^2E_1^2)n_2j_2ϵ_2|f(r)|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|(\frac{2c^2f^{}(r)}{r}+c^2\frac{\mathrm{\Delta }_{21}^{}}{2r^2}\beta f(r)c^2f^{\prime \prime }(r)2c^2f^{}(r)\frac{d}{dr}+\hfill \\ & \frac{c^2\mathrm{\Delta }_{21}^+\mathrm{\Delta }_{21}^{}}{4r^2}f(r)2ic\alpha _r[f^{}(r)+\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)]V(r))|n_1j_1ϵ_1;\hfill \end{array}$$
$`(28)`$
due to the presence of Dirac matrices in our results, we also require to calculate non-diagonal matrix elements for expressions involving $`\alpha _rf(r)`$ and $`\beta f(r)`$, namely

$$\begin{array}{cc}& H_2\left(i\alpha _rf(r)\right)=\hfill \\ & c\left[\frac{f(r)}{r}f^{}(r)f(r)\frac{d}{dr}+\frac{ϵ_2}{2r}\left(2j_2+1\right)\beta f(r)\right]+ic^2\alpha _r\beta f(r)i\alpha _rV(r)f(r),\hfill \end{array}$$
$`(29)`$
and

$$\begin{array}{cc}\hfill \left(i\alpha _rf(r)\right)H_1& =\hfill \\ & cf(r)\left[\frac{1}{r}\left(1+r\frac{d}{dr}\right)+\frac{ϵ_1}{2r}\left(2j_1+1\right)\beta \right]ic^2\alpha _r\beta f(r)i\alpha _rV(r)f(r);\hfill \end{array}$$
$`(30)`$
adding up these two last expressions, we get

$$\begin{array}{cc}& (E_2+E_1)n_2j_2ϵ_2|i\alpha _rf(r)|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|\frac{2cf(r)}{r}cf^{}(r)2cf(r)\frac{d}{dr}+c\frac{\mathrm{\Delta }_{21}^{}}{2r}\beta f(r)2i\alpha _rV(r)f(r)|n_1j_1ϵ_1.\hfill \end{array}$$
$`(31)`$
From the matrix element of $`H_2\left(i\alpha _rcf(r)\right)\left(i\alpha _rcf(r)\right)H_1`$, we can obtain

$$\begin{array}{cc}\hfill (E_2E_1)n_2j_2ϵ_2|& i\alpha _rf(r)|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|cf^{}(r)+c\frac{\mathrm{\Delta }_{21}^+}{2r}\beta f(r)+2c^2i\alpha _r\beta f(r)|n_1j_1ϵ_1;\hfill \end{array}$$
$`(32)`$
proceeding in a similar way for $`H_2\left(\beta f(r)\right)+\left(\beta f(r)\right)H_1`$, we get

$$\begin{array}{cc}\hfill (E_2+E_1)n_2j_2ϵ_2|\beta f(r)|n_1j_1ϵ_1=& n_2j_2ϵ_2|ic\beta \alpha _rf^{}(r)ic\alpha _r\frac{\mathrm{\Delta }_{21}^{}}{2r}f(r)\hfill \\ & +2\left[c^2+\beta V(r)\right]f(r)|n_1j_1ϵ_1.\hfill \end{array}$$
$`(33)`$
Equations (23–33) are the basic equations of our problem. To proceed, we consider, as in the non-relativistic case, radial functions of the form $`f(r)=r^\lambda `$ and insert the explicit expression for the Coulomb potential: $`V(r)=Z/r`$. Let us mention though that our results can be generalized to other power of potentials, such as the Lennard-Jones potentials .

Substituting $`f(r)=r^\lambda `$ in (28), it follows

$$\begin{array}{cc}\hfill \left(E_2^2E_1^2\right)& n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c^2\left[\frac{\mathrm{\Delta }_{21}^+\mathrm{\Delta }_{21}^{}}{4}\lambda \left(\lambda +1\right)\right]r^{\lambda 2}+c^2\frac{\mathrm{\Delta }_{21}^{}}{2}\beta r^{\lambda 2}2c^2\lambda r^{\lambda 1}\frac{d}{dr}+\hfill \\ & 2ic\alpha _r\left(\lambda +\frac{\mathrm{\Delta }_{21}^{}}{2}\beta \right)r^{\lambda 1}V(r)|n_1j_1ϵ_1;\hfill \end{array}$$
$`(34)`$
hence, we can eliminate the term containing the derivative operator in this last equation, using $`f(r)=r^{\lambda 1}`$ in Eq. (31), to get the result

$$\begin{array}{cc}\hfill \left(E_2^2E_1^2\right)& n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c^2\frac{\mathrm{\Delta }_{21}^+\mathrm{\Delta }_{21}^{}}{4}r^{\lambda 2}+c^2\frac{\mathrm{\Delta }_{21}^{}}{2}\beta \left(1\lambda \right)r^{\lambda 2}ic\alpha _r\beta \mathrm{\Delta }_{21}^{}r^{\lambda 1}V(r)+\hfill \\ & +\left(E_2+E_1\right)\lambda \left(ic\alpha _r\right)r^{\lambda 1}|n_1j_1ϵ_1;\hfill \end{array}$$
$`(35)`$
in this last equation, we use Eq. (23) to eliminate the term with $`ic\alpha _r\mathrm{\Delta }_{21}^{}\beta r^{\lambda 1}`$, to get

$$\begin{array}{cc}& (E_2^2E_1^2)n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1=n_2j_2ϵ_2|c^2\left[\frac{\mathrm{\Delta }_{21}^{}\mathrm{\Delta }_{21}^+}{4}+\frac{\mathrm{\Delta }_{21}^{}}{2}(1\lambda )\beta \right]r^{\lambda 2}+\hfill \\ & 2Z\left[ic\alpha _rr^{\lambda 2}(1\lambda )(E_2E_1)r^{\lambda 1}\right](E_2+E_1)\lambda ic\alpha _rr^{\lambda 1}|n_1j_1ϵ_1.\hfill \end{array}$$
$`(36)`$
Now, from Eq. (32) with $`f(r)=r^{\lambda 1}`$ we get

$$\begin{array}{cc}& (E_2E_1)n_2j_2ϵ_2|i\alpha _rr^{\lambda 1}|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c\left(\lambda 1\right)r^{\lambda 2}+c\frac{\mathrm{\Delta }_{21}^+}{2}\beta r^{\lambda 2}+2ic^2\alpha _r\beta mr^{\lambda 1}|n_1j_1ϵ_1\hfill \end{array}$$
$`(37)`$
and, using $`f(r)=r^\lambda `$ in Eq. (33) to eliminate the term $`2ic\alpha _r\beta mr^{\lambda 1}`$ from the above equation, we obtain

$$\begin{array}{cc}& (E_2E_1)n_2j_2ϵ_2|i\alpha _rr^{\lambda 1}|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c\left(\lambda 1\right)r^{\lambda 2}+c\frac{\mathrm{\Delta }_{21}^+}{2}\beta r^{\lambda 2}\frac{2c}{\lambda }\left(E_2+E_1\right)\beta r^\lambda +\frac{c^2}{\lambda }\left(i\alpha _r\right)\mathrm{\Delta }_{21}^{}r^{\lambda 1}+\hfill \\ & +\frac{4c^3}{\lambda }r^\lambda \frac{4cZ}{\lambda }\beta r^{\lambda 1}|n_1j_1ϵ_1;\hfill \end{array}$$
$`(38)`$
which can be written as

$$\begin{array}{cc}& \left[(E_2E_1)\frac{\mathrm{\Delta }_{21}^{}c^2}{\lambda }\right]n_2j_2ϵ_2|(i\alpha _rr^{\lambda 1})|n_1j_1ϵ_1=n_2j_2ϵ_2|c(\lambda 1)r^{\lambda 2}+\hfill \\ & \frac{4c^3}{\lambda }r^\lambda +c\frac{\mathrm{\Delta }_{21}^+}{2}\beta r^{\lambda 2}\frac{4Zc}{\lambda }\beta r^{\lambda 1}\frac{2c}{\lambda }(E_2+E_1)\beta r^\lambda |n_1j_1ϵ_1.\hfill \end{array}$$
$`(39)`$
We can also obtain a new relationship for the matrix elements of $`i\alpha _rr^{\lambda 1}`$, using Eq. (23) with $`f(r)=r^\lambda `$, and substitute the result in Eq. (37) to eliminate the term $`2i\alpha _r\beta mr^{\lambda 1}`$

$$\begin{array}{cc}& (E_2E_1)n_2j_2ϵ_2|i\alpha _rr^{\lambda 1}|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c\left(\lambda 1\right)r^{\lambda 2}+c\frac{\mathrm{\Delta }_{21}^+}{2}\beta r^{\lambda 2}+\frac{4c^2\lambda }{\mathrm{\Delta }_{21}^{}}\left(i\alpha _r\right)r^{\lambda 1}\hfill \\ & \frac{4c}{\mathrm{\Delta }_{21}^{}}\left(E_2E_1\right)r^\lambda |n_1j_1ϵ_1.\hfill \end{array}$$
$`(40)`$
Rearranging terms, we obtain

$$\begin{array}{cc}& \left[(E_2E_1)\frac{4c^2\lambda }{\mathrm{\Delta }_{21}^{}}\right]n_2j_2ϵ_2|(i\alpha _rr^{\lambda 1})|n_1j_1ϵ_1=\hfill \\ & n_2j_2ϵ_2|c(\lambda 1)r^{\lambda 2}\frac{4c}{\mathrm{\Delta }_{21}^{}}(E_2E_1)r^\lambda +c\frac{\mathrm{\Delta }_{21}^+}{2}\beta r^{\lambda 2}|n_1j_1ϵ_1.\hfill \end{array}$$
$`(41)`$
The relation we are looking for follows from this last result and Eq. (36). We use succesively $`r^{\lambda 1}`$ and $`r^{\lambda 2}`$ from Eq. (41) to eliminate the terms $`2(E_2+E_1)\lambda ic\alpha _rr^{\lambda 1}`$ and $`2ic\alpha _rr^{\lambda 2}(1\lambda )`$ that appear in Eq. (36) to finally get

$$\begin{array}{cc}\hfill c_0n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1=\underset{i=1}{\overset{3}{}}c_in_2j_2ϵ_2|r^{\lambda i}|n_1j_1ϵ_1+\underset{i=2}{\overset{3}{}}d_in_2j_2ϵ_2|\beta r^{\lambda i}|n_1j_1ϵ_1,& \end{array}$$
$`(42)`$
where the numbers $`c_i`$, $`i=0,\mathrm{}3`$ are given by

$$\begin{array}{cc}\hfill c_0& =\frac{(E_2^2E_1^2)(E_2E_1)\mathrm{\Delta }_{21}^{}}{(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2\lambda },\hfill \\ \hfill c_1& =\frac{2Z(E_2E_1)^2\mathrm{\Delta }_{21}^{}}{(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2(\lambda 1)},\hfill \\ \hfill c_2& =c^2\frac{\mathrm{\Delta }_{21}^{}\mathrm{\Delta }_{21}^+}{4}c^2\lambda (\lambda 1)\frac{(E_1+E_2)\mathrm{\Delta }_{21}^{}}{(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2\lambda },\hfill \\ \hfill c_3& =\frac{2Zc^2(\lambda 1)(\lambda 2)\mathrm{\Delta }_{21}^{}}{(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2(\lambda 1)},\hfill \end{array}$$
$`(43)`$
and the numbers $`d_i`$, $`i=2`$ and 3, by

$$\begin{array}{cc}\hfill d_2& =c^2\frac{\mathrm{\Delta }_{21}^{}}{2}\left[(1\lambda )+\frac{\lambda (E_2+E_1)\mathrm{\Delta }_{21}^+}{(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2\lambda }\right],\hfill \\ \hfill d_3& =\frac{Zc^2(\lambda 1)\mathrm{\Delta }_{21}^{}\mathrm{\Delta }_{21}^+}{(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2(\lambda 1)}.\hfill \end{array}$$
$`(44)`$
As we may have expected, we need to know six matrix coefficients instead of only three as in the non-relativistic case. This is a consequence of the fact that, in the Dirac case, we have to deal with the big and the small components in the state function, doubling in this sense the “degrees of freedom” of the system.

It does not seems to be possible to avoid the $`\beta `$-dependency in Eq. (44), and thus, taken on its own, Eq. (41) does not allow the computation of $`n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1`$ in terms of the $`n_2j_2ϵ_2|r^{\lambda a}|n_1j_1ϵ_1`$, $`a=1,2,3`$. The situation is not hopeless though because it is still possible to obtain another recurrence relation for non-diagonal matrix elements of $`\beta r^\lambda `$ simply by eliminating the term $`i\alpha _rr^{\lambda 1}`$ between Eqs. (39) and (41). In such a way we get

$$\begin{array}{cc}\hfill e_0n_2j_2ϵ_2|\beta & r^\lambda |n_1j_1ϵ_1=b_0n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1+b_2n_2j_2ϵ_2|r^{\lambda 2}|n_1j_1ϵ_1\hfill \\ & +e_1n_2j_2ϵ_2|\beta r^{\lambda 1}|n_1j_1ϵ_1+e_2n_2j_2ϵ_2|\beta r^{\lambda 2}|n_1j_1ϵ_1,\hfill \end{array}$$
$`(45)`$
where the numbers $`b_i`$ and $`e_i`$ $`i=1,2,3`$ are given by

$$\begin{array}{cc}\hfill b_0=& 4\lambda \left[(E_2E_1)^24c^4\right],\hfill \\ \hfill b_2=& c^2(1\lambda )\left[(\mathrm{\Delta }_{21}^{})^24\lambda ^2\right],\hfill \\ \hfill e_0=& 2(E_2+E_1)[(E_2E_1)\mathrm{\Delta }_{21}^{}4c^2\lambda ],\hfill \\ \hfill e_1=& 4Z[4c^2\lambda (E_2E_1)\mathrm{\Delta }_{21}^{}],\hfill \\ \hfill e_2=& c^2\frac{\mathrm{\Delta }_{21}^+}{2}[(\mathrm{\Delta }_{21}^{})^24\lambda ^2].\hfill \end{array}$$
$`(46)`$
Equations (42) and (45) together are the useful recurrence relations in the relativistic Dirac case.

IV. The diagonal case $`\mathrm{\Delta }_{21}^{}=0`$ ($`j_2=j_1`$, $`ϵ_2=ϵ_1`$).

In the results of the last section we always assume $`\mathrm{\Delta }_{21}^{}0`$, but in order to study the diagonal case we must have $`ϵ_1=ϵ_2`$ and $`j_1=j_2`$; this in turn imply $`\mathrm{\Delta }_{21}^{}=0`$ and (as always!) $`\mathrm{\Delta }_{21}^+\mathrm{\Delta }^+0`$. To deal with the diagonal case we start all over again. The equation set for this case is particularly simple, first from Eq. (23) we have

$$\begin{array}{cc}\hfill (E_2E_1)n_2jϵ|f(r)|n_1jϵ& =n_2jϵ|(ic\alpha _rf^{}(r)|n_1jϵ,\hfill \end{array}$$
$`(47)`$
then we can procced to calculate the second order iteration by substituting, as in the previous section, $`f(r)\xi _{}=H_2f(r)f(r)H_1`$ in (47) to obtain

$$\begin{array}{cc}\hfill (E_2E_1)^2n_2jϵ|f(r)|n_1jϵ=n_2jϵ|& c^2f^{\prime \prime }(r)+c^2\frac{\mathrm{\Delta }^+}{2r}f^{}(r)\beta +\hfill \\ & 2ic^3\alpha _r\beta f^{}(r)|n_1jϵ;\hfill \end{array}$$
$`(48)`$
and then substitute $`f(r)\xi _+=H_2f(r)+f(r)H_1`$ again in (47) to get instead

$$\begin{array}{cc}\hfill (E_2^2E_1^2)n_2jϵ|f(r)|n_1jϵ=n_2jϵ|& \frac{2c^2f^{}(r)}{r}c^2f^{\prime \prime }(r)2c^2f^{}(r)\frac{d}{dr}\hfill \\ & 2ic\alpha _rf^{}(r)V(r)|n_1jϵ.\hfill \end{array}$$
$`(49)`$
The equations equivalent of Eqs. (31–33) are in this case

$$\begin{array}{cc}\hfill (E_2+E_1)n_2jϵ|(i\alpha _rf(r))|n_1jϵ=n_2jϵ|& \frac{2cf(r)}{r}cf^{}(r)2cf(r)\frac{d}{dr}\hfill \\ & 2i\alpha _rV(r)f(r)|n_1jϵ,\hfill \end{array}$$
$`(50)`$
and

$$\begin{array}{cc}\hfill (E_2E_1)n_2jϵ|(i\alpha _rf(r))|n_1jϵ=n_2jϵ|& cf^{}(r)+\frac{c\mathrm{\Delta }^+}{2r}\beta f(r)+\hfill \\ & 2i\alpha _r\beta c^2f(r)|n_1jϵ.\hfill \end{array}$$
$`(51)`$
We also have, for the matrix elements of $`\beta f(r)`$,

$$\begin{array}{cc}\hfill (E_2+E_1)n_2jϵ|\beta f(r)|n_1jϵ=n_2jϵ|& ic\alpha _r\beta f^{}(r)+\hfill \\ & 2\left[c^2+\beta V(r)\right]f(r)|n_1jϵ.\hfill \end{array}$$
$`(52)`$
These expressions are the basic equations for the case $`\mathrm{\Delta }_{21}^{}=0`$.

We can now obtain a recurrence relation valid in the diagonal case. First, let us use $`f(r)=r^\lambda `$ in Eq. (48) to get

$$\begin{array}{cc}\hfill (E_2E_1)^2n_2jϵ|r^\lambda |n_1jϵ=& \lambda n_2jϵ|c^2(\lambda 1)r^{\lambda 2}+c^2\frac{\mathrm{\Delta }^+}{2}\beta r^{\lambda 2}+\hfill \\ & 2ic^3\alpha _r\beta r^{\lambda 1}|n_1jϵ.\hfill \end{array}$$
$`(53)`$
Evaluating now equation (52) with $`f(r)=r^\lambda `$, we obtain

$$\begin{array}{cc}\hfill (E_2+E_1)n_2jϵ|\beta r^\lambda |n_1jϵ=& n_2jϵ|ic\alpha _r\beta \lambda r^{\lambda 1}\hfill \\ & +2\left(c^2\frac{Z\beta }{r}\right)r^\lambda |n_1jϵ,\hfill \end{array}$$
$`(54)`$
and eliminating the $`ic\alpha _r\beta \lambda r^{\lambda 1}`$ between Eqs. (53) and (54), we finally get

$$\begin{array}{cc}& \left[(E_2E_1)^24c^4\right]n_2jϵ|r^\lambda |n_1jϵ=\lambda c^2\frac{\mathrm{\Delta }_{21}^+}{2}n_2jϵ|\beta r^{\lambda 2}|n_1jϵ\hfill \\ & 4Zc^2n_2jϵ|\beta r^{\lambda 1}|n_1jϵ2c^2(E_2+E_1)n_2jϵ|\beta r^\lambda |n_1jϵ\hfill \\ & c^2\lambda (\lambda 1)n_2jϵ|r^{\lambda 2}|n_1jϵ.\hfill \end{array}$$
$`(55)`$
This is the only recurrence relation we get in the diagonal case. To “close” the relation we can use the diagonal recurrence relations given in .

The special case when $`\lambda =0`$ is of particular interest

$$\begin{array}{cc}\hfill \left[(E_2E_1)^24c^4\right]\delta _{n_1n_2}& =4Zc^2n_2jϵ|\frac{\beta }{r}|n_1jϵ\hfill \\ & 2c^2(E_2+E_1)n_2jϵ|\beta |n_1jϵ.\hfill \end{array}$$
$`(56)`$
This expression could be considered as a relativistic generalization of the Pasternak-Sternheimer rule of non relativistic quantum mechanics (Equation (8) of section II) , which says that the expectation value between hydrogenic states of the $`1/r^2`$ potential, vanishes when the orbital angular momenta of the states $`1`$ and $`2`$ coincide, i.e. when $`l_1=l_2`$. In the relativistic case the expectation value of the $`\beta /r`$ potential (which could be regarded as the square root of $`1/r^2`$ including both signs), does not necessarily vanish even when the total angular momenta of the two states coincide: i.e. it does not vanish when $`j_1=j_2`$. Again, this agrees with the fact that the non-relativistic Pasternack-Sternheimer rule is applicable to eigenfunctions of potentials whose energy eigenvalues depend only on the principal quantum number—which is not the case for the hydrogen atom in Dirac relativistic quantum mechanics .

Moreover, two special cases are immediately deduced from this last expression (56):

1) The first case, when $`n_1n_2`$, is

$$n_2jϵ|\frac{Z\beta }{r}|n_1jϵ=\frac{1}{2}(E_2+E_1)n_2jϵ|\beta |n_1jϵ.$$
$`(57)`$
2) The other case follows when $`n_1=n_2`$

$$c^2=\beta V(r)+E\beta =Z\frac{\beta }{r}+E\beta ,$$
$`(58)`$
which is the relativistic virial theorem ; from the relation $`c^2<\beta >=E`$ , we can also put it in the alternative form

$$E^2=c^2\beta V(r)+c^4=c^2Z\frac{\beta }{r}+c^4.$$
$`(59)`$
V. The values of $`<r^\lambda >`$ and $`<\beta r^\lambda >`$.

The recurrence relations found above, involve in principle simple expressions (since they involve only matrix elements of Dirac hydrogenic states) that can be burdensome to handle. Given such situation, we have also calculated explicit formulas that are needed to evaluate the diagonal and the non-diagonal matrix elements of interest. The expressions are related to the hypergeometric function and can be deduced from the two differential equations that follow from the Hamiltonian (20), as it is shown in the Appendix. In particular, from Eq. (A.15) we calculate $`<r^\lambda >`$ and $`<\beta r^\lambda >`$. We quote the results here and refer to the Appendix for the details.

$$<r^\lambda >=\frac{mc^2|C|^2}{(2k)^{\lambda +1}2^{s1}}\left[I_{nn}^{2s}(\lambda )u^2+I_{n1n1}^{2s}(\lambda )v^2+EuvI_{nn1}^{2s}(\lambda )\right],$$
$`(60a)`$
and

$$<\beta r^\lambda >=\frac{E|C|^2}{(2k)^{\lambda +1}2^{s1}}\left[I_{nn}^{2s}(\lambda )u^2+I_{n1n1}^{2s}(\lambda )v^2+mc^2uvI_{nn1}^{2s}(\lambda )\right];$$
$`(60b)`$
in these expressions $`n=0,\mathrm{\hspace{0.17em}1},\mathrm{\hspace{0.17em}2},\mathrm{}`$, and

$$\begin{array}{cc}\hfill k\frac{1}{\mathrm{}c}& \sqrt{m^2c^4E^2},\zeta \frac{Ze^2}{\mathrm{}c}=Z\alpha _F,\tau _jϵ(j+\frac{1}{2}),\hfill \\ & \\ & \nu \sqrt{\frac{mc^2E}{mc^2+E}},s\sqrt{\tau _j^2\zeta ^2},\hfill \end{array}$$
$`(61)`$
where $`\alpha _F1/137`$ is the fine structure constant and the $`I_{nm}^{2s}(\lambda )`$ symbols are defined in equation (A.15) of the Appendix. The numbers $`u`$ and $`v`$ are constants such that

$$u=(\tau _j+s+n\zeta \nu ^1)^{1/2},v=(n+2s)(\tau _j+s+n\zeta \nu ^1)^{1/2};$$
$`(62)`$
in the Appendix we give a simple proof of this result. Notice that in this section we have explicitly written $`\mathrm{}`$, $`e`$, and $`c`$ in our results. Finally, to obtain $`C`$, we use relations (61) to get $`(\tau _j+s+n\zeta \nu ^1)^1=(n+s\tau _j\zeta \nu ^1)/n(n+2s)`$; we need also $`(n+s)=\zeta E/\sqrt{m^2c^4E^2}`$, which is obtained from the expression for the energy eigenvalues of the Dirac hydrogen atom:

$$E=mc^2\left(1+\frac{Z^2\alpha _F^2}{\left(nj1/2+\sqrt{(j+1/2)^2Z^2\alpha _F^2}\right)^2}\right)^{1/2};$$
$`(63)`$
elementary algebra gives then the result

$$|C|=\frac{\mathrm{}\mathrm{\hspace{0.17em}2}^{s1}}{Z\alpha c^2}\sqrt{\frac{n!k}{2m^3}}\left[\mathrm{\Gamma }(n+2s+1)\right]^{1/2}.$$
$`(64)`$
where we have written explicitly the dimensional factors.

Acknowledgements.

This work has been partially supported by CONACyT. It is a pleasure to thank C. Cisneros for all the collaboration, and V. M. Shabaev for making us aware of Ref. 15. ALSB and HNNY acknowledge the help of F. C. Minina, B. Caro, M. X’Sac, M. Osita, Ch. Dochi, F. C. Bonito, G. Abdul, C. Sabi, C. F. Quimo, S. Mahui, R Sammi, M. Mati, U. Becu, Q. Chiornaya, E. Hera and M. Sieriy. Last but not least, this paper is dedicated to the memory of our beloved friends Q. Motita, B. Kuro, M. Mina, Ch Cori, C. Ch. Ujaya, Ch. Mec, F. Cucho, R. Micifuz and U. Kim.

Appendix. Explicit expressions for relativistic matrix elements of $`r^\lambda `$ and $`\beta r^\lambda `$

It is possible to obtain explicit expressions for the diagonal and non diagonal matrix elements in the case $`V(r)=Z/r.`$ The purpose of this appendix is to give the basic relation that is needed for such evaluation. As we heavily draw from results previously obtained, in this section we use the notation of Ref. 23, in particular $`\mathrm{}=c=e=1`$, though we sometimes write all the dimensional constants.

We are interested in the bound states of the problem, so the quantity $`k\sqrt{m^2E^2}`$ is positive. We can write the differential equations for the radial part of any central problem in terms of the dimensionless variable $`\rho kr`$  and the symbols defined in (60)

$$\begin{array}{cc}\hfill \left(\frac{d}{d\rho }+\frac{\tau _j}{\rho }\right)G(\rho )& =\left(\nu +\frac{\zeta }{\rho }\right)F(\rho ),\hfill \\ \hfill \left(+\frac{d}{d\rho }+\frac{\tau _j}{\rho }\right)F(\rho )& =\left(\nu ^1+\frac{\zeta }{\rho }\right)G(\rho );\hfill \end{array}$$
$`(A1)`$
where we look for solutions of the form

$$F(\rho )=\sqrt{m+E}\left[\psi _{}(\rho )+\psi _+(\rho )\right],$$
$`(A2)`$
$$G(\rho )=\sqrt{mE}\left[\psi _{}(\rho )\psi _+(\rho )\right].$$
$`(A3)`$
The solution to these coupled differential equations can be written in terms of the Laguerre polynomials of non-integer index

$$\begin{array}{cc}\hfill \psi _+(\rho )=& a\rho ^s\mathrm{exp}(\rho )_{n1}^{2s}(2\rho ),\hfill \\ \hfill \psi _{}(\rho )=& b\rho ^s\mathrm{exp}(\rho )_n^{2s}(2\rho ),\hfill \end{array}$$
$`(A4)`$
where the Laguerre polynomials $`_n^\alpha (\rho )`$ are related to both the hypergeometric function, $`{}_{1}{}^{}F_{1}^{}(n,\alpha +1;\rho )`$, and the Sonine polynomials, $`T_\alpha ^{(n)}(\rho )`$ , through the relation

$$_n^\alpha (\rho )=\frac{\mathrm{\Gamma }(\alpha +n+1)}{n!\mathrm{\Gamma }(\alpha +1)}{}_{1}{}^{}F_{1}^{}(n;\alpha +1;\rho )=(1)^n\mathrm{\Gamma }(\alpha +n+1)T_\alpha ^{(n)}(\rho ),$$
$`(A5)`$
and $`a`$ and $`b`$ are constants. Substitution of these results in Eq. (A1) gives the condition

$$\begin{array}{cc}\hfill a(\tau _j+s\zeta \nu ^1+n)+b(n+2s)& =0,\hfill \\ \hfill b(\tau _js+\zeta \nu ^1n)an& =0.\hfill \end{array}$$
$`(A6)`$
Solving these last two equations give us a relationship between $`n`$ and $`\nu `$. From Eq. (45) we see that we can solve for the energy $`E`$ and obtain the relativistic energy spectrum (63), provided we first introduce the principal quantum number $`Nj+1/2+n`$. To proceed further, we take

$$b=a(\tau _j+s+n\zeta \nu ^1)/(n+2s),$$
$`(A7)`$
and write the result in a symmetrized form:

$$\begin{array}{cc}\hfill F(\rho )& =\sqrt{mc^2+E}C\rho ^se^\rho \left[u_n^{2s}(2\rho )+v_{n1}^{2s}(2\rho )\right],\hfill \\ \hfill G(\rho )& =\sqrt{mc^2E}C\rho ^se^\rho \left[u_n^{2s}(2\rho )v_{n1}^{2s}(2\rho )\right],\hfill \end{array}$$
$`(A8)`$
where

$$u=(\tau _j+s+n\zeta \nu ^1)^{1/2},v=(n+2s)(\tau _j+s+n\zeta \nu ^1)^{1/2},$$
$`(A9)`$
$`C`$ is a normalization constant that can be obtained from

$$_0^{\mathrm{}}e^xx^\alpha _n^\alpha (x)_m^\alpha (x)=\delta _{mn}\frac{\mathrm{\Gamma }(n+\alpha +1)}{n!};$$
$`(A10)`$
after some work we obtain

$$|C|=\frac{\mathrm{}\mathrm{\hspace{0.17em}2}^{s1}}{Z\alpha c^2}\sqrt{\frac{n!k}{2m^3}}\left[\mathrm{\Gamma }(n+2s+1)\right]^{1/2}.$$
$`(A11)`$
We can also calculate the expectation values for diagonal and non diagonal matrix elements. For diagonal, arbitrary power matrix elements of the form $`<r^\lambda >`$ and $`<\beta r^\lambda >`$, we need to calculate the expression

$$I_{nm}^\alpha (\lambda )=_0^{\mathrm{}}e^xx^{\alpha +\lambda }_n^\alpha (x)_m^\alpha (x)𝑑x.$$
$`(A12)`$
This expression converges for $`Re(\alpha +\lambda +1)>0`$, and is zero if $`\lambda `$ is an integer such that $`mn>\lambda 0,`$ where without loss of generality, we assume that $`m>n`$. From Rodrigues formula and $`(d^m/dx^m)x^{k+\lambda }=(1)^m[k\lambda ]_mx^{k+\lambda m}`$, where $`[n]`$, $`n`$ an integer, is a Pochhammer symbol , we find, after a $`m`$-times partial integration,

$$I_{nm}^\alpha (\lambda )=\frac{1}{m!}\underset{k=0}{\overset{n}{}}(1)^k\frac{\mathrm{\Gamma }(n+\alpha +1)\mathrm{\Gamma }(\alpha +k+\lambda +1)[k\lambda ]_m}{k!(nk)!\mathrm{\Gamma }(\alpha +k+1)}.$$
$`(A13)`$
We use now the identity $`[k\lambda ]_m=[k\lambda ]_k[\lambda ]_{mk},`$ change the order of summation $`knk`$ and use the identities

$$\begin{array}{cc}\hfill [\lambda ]_{mn+k}& =[\lambda ]_{mn}[\lambda +mn]_k,\hfill \\ \hfill \mathrm{\Gamma }(n+\alpha +1)& =(1)^k\mathrm{\Gamma }(\alpha +nk+1)[\alpha n]_k,\hfill \\ \hfill \mathrm{\Gamma }(\alpha +\lambda ++n+1)& =(1)^k\mathrm{\Gamma }(\alpha +\lambda +nk+1)[\alpha \lambda n]_k,\hfill \\ \hfill [kn\lambda ]_{nk}& =(1)^n\frac{\mathrm{\Gamma }(\lambda +n+1)}{\mathrm{\Gamma }(\lambda +1)}\frac{1}{[\lambda n]_k},\hfill \end{array}$$
$`(A14)`$
to obtain that

$$\begin{array}{cc}& I_{nm}^\alpha (\lambda )=\hfill \\ & [\lambda ]_{mn}\frac{\mathrm{\Gamma }(\alpha +\lambda +n+1)\mathrm{\Gamma }(\lambda +n+1)}{m!n!\mathrm{\Gamma }(\lambda +1)}\hfill \\ & {}_{3}{}^{}F_{2}^{}(\alpha n,\lambda +mn,n;\lambda n,\alpha \lambda n;1).\hfill \end{array}$$
$`(A15)`$
We consider two cases for the general matrix elements $`n_2j_2ϵ_2|r^\lambda |n_1j_1ϵ_1`$ and $`n_2j_2ϵ_2|\beta r^\lambda |n_1j_1ϵ_1`$; the first one, when $`k_1=k_2`$, where we need to evaluate

$$K_{nn}^{s_1s_2}(\lambda )=_0^{\mathrm{}}x^{s_1+s_2+\lambda }e^x_n^{(2s_1)}(x)_m^{(2s_2)}(x)𝑑r,$$
$`(A16)`$
and the second one, when $`k_1k_2`$, where we need

$$K_{nm}^{s_1s_2}(\lambda )=_0^{\mathrm{}}r^{s_1+s_2+\lambda }e^{(k_1+k_2)r}_n^{(2s_1)}(2k_1r)_m^{(2s_2)}(2k_2r)𝑑r.$$
$`(A17)`$
In the first case, we see that integral (A16) is convergent if $`Re(s_1+s_2+\lambda +1)>0,`$ and vanishes when $`s_1s_2+\lambda `$ is an integer such that $`mn>s_1s_2+\lambda 0`$. Using a similar reasoning as in the diagonal case, we get

$$\begin{array}{cc}& K_{nm}^{s_1s_2}(\lambda )=\hfill \\ & [\lambda +s_2s_1]_{mn}\frac{\mathrm{\Gamma }(s_1+s_2++\lambda +n+1)\mathrm{\Gamma }(\lambda +s_1s_2+n+1)}{m!n!\mathrm{\Gamma }(\lambda +s_1s_2+1)}\hfill \\ & {}_{3}{}^{}F_{2}^{}(2s_1n,\lambda +s_2s_1+mn,n;\lambda +s_2s_1n,\lambda s_1s_2n;1).\hfill \end{array}$$
$`(A18)`$
In the second case, the integral converges for $`Re(s_1+s_2+\lambda +1)>0,`$ and is not zero provided $`k_1k_2.`$ A straightforward calculation by parts shows that

$$\begin{array}{cc}\hfill K_{nm}^{s_1s_2}(\lambda )& =\underset{j=0}{\overset{n}{}}\underset{i=0}{\overset{m}{}}\frac{(1)^j(k_2k_1)^{mi}(k_1+k_2)^{(ims_1s_2\lambda 1)}}{i!j!(mi)!(nj)!}\hfill \\ & \frac{\mathrm{\Gamma }(n+2s_1+1)[s_2s_1\lambda j]_i}{\mathrm{\Gamma }(2s_1+j+1)}\mathrm{\Gamma }(m+s_2+s_1+\lambda i+1),\hfill \end{array}$$
$`(A19)`$
where $`k_1k_2.`$ Although less practical than the other expressions found here, we still can rewrite Eq. (A19) in a different form using the well known identities

$$\begin{array}{cc}& [p]_{mi}=(1)^{mi}\frac{\mathrm{\Gamma }(p+1)}{[pm+1]_i\mathrm{\Gamma }(pm+1)},\hfill \\ & \mathrm{\Gamma }(pm+i+1)=[pm+1]_i\mathrm{\Gamma }(pm+1),\hfill \\ & (mi)!=\frac{m!(1)^i}{[m]_i},\hfill \\ & \mathrm{\Gamma }(p+1)=[pm+1]_m\mathrm{\Gamma }(pm+1).\hfill \end{array}$$
$`(A20)`$
for any number $`p`$ and $`m`$ and $`i`$ integers. After some algebra, we finally get

$$\begin{array}{cc}& K_{nm}^{s_1s_2}(\lambda )\hfill \\ & =\frac{(1)^m\mathrm{\Gamma }(n+2s_1+1)\mathrm{\Gamma }(s_1+s_2+\lambda +1)}{m!(k_2+k_1)^{s_1+s_2+\lambda +1}}\underset{j=0}{\overset{n}{}}\frac{(1)^j[s_1s_2+\lambda +jm+1]_m}{j!(nj)!\mathrm{\Gamma }(2s_1+j+1)}\hfill \\ & \times {}_{2}{}^{}F_{1}^{}(m,s_1+s_2+\lambda +1;s_1s_2+\lambda +jm+1;\frac{k_2k_1}{k_2+k_1}).\hfill \end{array}$$
$`(A21)`$
References

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# Vanishing Hall Constant in the Stripe Phase of Cuprates

\[

## Abstract

The Hall constant $`R_H`$ is considered for the stripe structures. In order to explain the vanishing of $`R_H`$ in La2-y-xNdySrxCuO4 at $`x=1/8`$, we use the relation of $`R_H`$ to the Drude weight $`D`$ as well as direct numerical calculation, to obtain results within the $`t`$-$`J`$ model, where the stripes are imposed via a charge potential and a staggered magnetic field. The origin of $`R_H0`$ is related to a maximum in $`D`$ and the minimal kinetic energy in stripes with a hole filling $`1/2`$. The same argument indicates on a possibility of $`R_H0`$ in the whole range of static stripes for $`x1/8`$.

\]

The evidence for the stripe structures in La2-y-xNdySrxCuO4 (LNSCO) emerging from neutron scattering experiments  has stimulated in recent years numerous experimental and theoretical investigations, trying to relate this phenomenon to superconductivity and other anomalous properties of cuprates. In the commensurate case $`x1/8`$ the stripe structure represents spin and charge ordering, i.e., domain walls within an ordered two-dimensional antiferromagnet (AFM) with the filling of $`n_l=N_h/L=1/2`$ hole per unit length (quarter filling in the usual band picture) within each domain wall - stripe. Actually, it was shown in the recent angle-resolved photoemission spectroscopy experiments that the stripes are in the quarter filled state . In contrast to many other systems showing spin-density wave and charge-density wave order at low temperatures, the stripe structures in cuprates appear to be metallic . This can be explained with charge carriers - holes being well mobile along the one-dimensional (1D) stripes. Recently, a systematic study of LNSCO ($`y=0.6`$) with varying doping $`x`$  revealed a striking signature of stripes in the behavior of the Hall constant $`R_H`$. While for $`x>0.15`$ $`R_H(x,T)`$ is very close to that of the reference doped La2-xSrxCuO4 (LSCO), $`R_H`$ appears to be very sensitive to the structural phase transition between the low-temperature tetragonal (LTT) and orthorhombic (LTO) phase for $`x<0.15`$. Below the LTT-LTO transition $`R_H`$ becomes strongly $`T`$ and $`x`$ dependent and it eventually vanishes, $`R_H0`$, at $`T0`$ for $`x0.12`$, i.e., in the structure with long range stripe order. At the same time the anomaly is weakly pronounced in the planar resistivity $`\rho _{ab}`$ .

In the present paper, we investigate $`R_H`$ in stripe structures and in particular a possible explanation for its vanishing. $`R_H0`$ in a conducting system is quite unusual and non universal. For instance, it could happen in an ordinary metal due to (accidental) cancellation of band curvatures or due to band crossings. However, cuprates are closer to hole-doped Mott insulators where in the reference LSCO a (semiconductor-like) semi-classical $`R_H1/x`$ is followed in a wide range $`x<0.2`$ at low $`T`$. $`R_H0`$ in LNSCO at $`x1/8`$ is, on the other hand, a very pronounced deviation from the latter. Therefore, one can speculate on more fundamental origin of this most pronounced macroscopic effect of stripes whereby the strong correlations play an essential role. The authors  interpreted the experimental finding $`R_H0`$ as an evidence for a transport along independent stripes. This requires exclusively 1D transport and therefore can hardly apply. Hall constant can be expressed in terms of planar conductivities $`\sigma _{\alpha \beta }`$ in a finite magnetic field $`B`$ as $`R_H=\sigma _{xy}/[B\sigma _{xx}\sigma _{yy}]`$. Assuming a very anisotropic system with stripes, e.g., along the $`x`$ direction and large $`\sigma _{xx}`$, it is plausible that $`\sigma _{xy}`$ scales with the weak hopping between stripes. But $`\sigma _{yy}`$ is expected usually to scale in the same way leaving the ratio $`R_H`$ finite. The evidence for the latter behavior can be found in the experiments on very anisotropic quasi-1D metals which reveal nevertheless quite normal metallic values of $`R_H`$ .

Another simple interpretation is that in a stripe structure with hole filling $`n_l=1/2`$ we are dealing along the single stripe with an equal concentration of holes and electrons, leading to the cancellation of $`\sigma _{xy}`$ while both diagonal $`\sigma _{\alpha \alpha }`$ remain finite. Although it is hard to improve this argument into a more formal theory, to some extent it seems to be closer to our final conclusions further on.

It is evident that the Hall effect in cuprates , as well as in systems with strongly correlated electrons in general, still lacks proper theoretical understanding. This applies for most investigated reference cuprate LSCO and $`R_H`$ dependence on $`T`$ and hole doping $`n_h`$. While the theoretical formulation of the Hall linear response $`R_H(\omega ,T)`$ is well established , there are very few theoretical results and numerical studies for models with strong correlation in particular in the relevant low $`T`$ and low doping regime . Recently an approach and a numerical procedure have been designed  which yield for a static d.c. $`R_H`$ at $`T=0`$ (although for a ladder system) the desired result, namely a semi-classical behavior $`R_H^{}=1/e_0n_h`$ in a magnetic insulator at low hole doping $`n_h=N_h/N`$ ($`e_0`$ being the electric charge), as found experimentally in cuprates . Moreover, for a reactive (non-dissipative) $`R_H(T=0)`$  it was possible to find an useful relation to the variation of the Drude weight (charge stiffness) $`D`$ with the electron density $`n`$,

$$R_H=\frac{1}{e_0D}\frac{D}{n}.$$
(1)
The latter relation is derived using the non-standard limit: $`\omega 0`$ first, then $`q0`$. Nevertheless, it has very attractive properties for the analysis of strongly correlated electrons: a) $`D`$ at $`T=0`$ is the central quantity distinguishing the Mott-Hubbard insulator from a conductor, b) close to the Mott insulator $`Dn_h=1n`$ directly implies a plausible semi-classical result $`R_H^{}=1/e_0n_h`$, which is hard to be established by other methods. While so far the relation has not been justified for the general case in the proper transport limit ($`q0`$ first, then $`\omega 0`$) it appears to be valid for a strongly anisotropic system where $`D=D_{\alpha \alpha }`$ should be taken along the most conducting direction $`\alpha `$ .

There is also a qualitative similarity of the relation (1) with the proposal in Ref. where the authors correlate Hall ($`B>0`$) conductivity $`\sigma _{xy}`$ with the doping dependence of the kinetic energy, i.e., $`K/n`$. Note that in a (tight binding) strongly correlated system $`K`$ and $`D`$ are related through the sum rule

$$ND_{\alpha \alpha }=\frac{1}{2}K_{\alpha \alpha }\frac{1}{e_0^2}_0^{\mathrm{}}\sigma _{\alpha \alpha }^{reg}(\omega )𝑑\omega ,$$
(2)
where $`\sigma ^{reg}`$ is the regular part of the optical conductivity and $`K_{\alpha \alpha }`$ involves only the hopping in the $`\alpha `$ direction.

Theoretical modeling of stripes in cuprates has proven to be quite delicate just due to their $`n_l=1/2`$ filling and metallic character. Stripe solutions of relevant (Hubbard and analogous) models within simplest mean-field approximations generally show a tendency towards $`n_l=1`$ filling and an insulating behavior. More recently extensive numerical analyses within the relevant $`t`$-$`J`$ model  confirm the relative stability of metallic stripes at commensurate doping $`n_h=1/8`$. These results and other approaches  all indicate a crucial interplay of the hole kinetic energy and the spin Heisenberg interaction in metallic stripes, both being crucially related to strong electron correlation.

Equation (1) suggests an explanation of $`R_H0`$ in $`x=1/8`$ stripes, namely that $`D(n)`$ is a local maximum for $`n_l=1/2`$, this being closely related to the minimum kinetic energy $`K`$ in this configuration. In order to support this conjecture we perform a numerically exact-diagonalization study of $`D`$ and $`R_H`$ within the prototype $`t`$-$`J`$ model,

$$H=t\underset{ijs}{}(\stackrel{~}{c}_{js}^{}\stackrel{~}{c}_{is}+\mathrm{H}.\mathrm{c}.)+J\underset{ij}{}(𝐒_i𝐒_j\frac{1}{4}n_in_j),$$
(3)
where no double occupancy of sites is allowed. In numerical studies we use $`J/t=0.4`$ to be in the strong-correlation regime relevant to cuprates.

Since studied systems are too small to inherently reproduce stripes, we impose them through an attractive hole potential $`V`$ along the stripe  and the staggered field $`h_i=\pm h`$ forming an AFM phase boundary across the stripe ,

$$H_{st}=V\underset{ist}{}(1n_i)+\underset{ist}{}h_iS_i^z.$$
(4)
First we consider numerically a system with $`N=4\times 4`$ sites and periodic boundary conditions (p.b.c.) in both the $`x`$ and $`y`$ directions. Two stripes are imposed along the $`x`$-direction with the inter-stripe distance $`d_0=2`$. $`D_{xx}=D`$ in such a system can be evaluated by introducing a flux through the torus modifying $`t\stackrel{~}{t}_{ij}=t\mathrm{exp}[i\theta (x_ix_j)]`$ to find an absolute energy minimum $`E^0(\theta )`$ at $`\theta =\theta _0`$ and then by taking the second derivative, i.e., $`D=(1/2N)^2E^0(\theta )/\theta ^2|_{\theta =\theta _0}`$. In Figs. 1(a) and (b), we present results for $`D`$ as a function of hole doping $`n_h`$ (only even $`N_h`$ are considered) and various stripe potentials $`V`$, without the staggered field $`h=0`$ as well as with $`h/t=0.4`$. Two limits for $`D(n_h)`$ are quite easy to understand. For $`V=0`$ we are dealing with a homogeneous 2D $`t`$-$`J`$ model where $`D`$ reaches maximum at $`n_h0.5`$. On the other hand, for large $`Vt`$ holes are localized to a 1D motion within each stripe. As in 1D, $`D`$ then reaches the maximum for stripe filling $`n_l=1/2`$, i.e., for $`n_h=1/(2d_0)=0.25`$ (while $`D0`$ for $`n_l1`$). Using Eq.(1) in the latter case clearly leads to $`R_H0`$ for stripes at $`n_l=1/2`$. Our results in Fig. 1(a) suggest that the maximum remains pronounced also for far more modest $`Vt`$. The introduction of the staggered field $`h`$, as shown in Fig. 1(b), enhances but also flattens the maximum which is visible now even at $`V/t0.5`$.

For comparison we present in Fig. 2 the related variation of $`K_{xx}`$ with $`n_h`$. We notice that in analogy to $`D`$ there is a maximum at $`n_l1/2`$, however well pronounced only for larger $`V/t`$ whereby $`K_{xx}`$ is also less sensitive to $`h`$.

By considering the $`t`$-$`J`$ model with open boundary conditions (o.b.c.) in the $`y`$ direction, i.e., on a ladder system $`N=L\times M`$, one can study $`R_H`$ even more directly . If we introduce the Hall electric field in the $`y`$-direction as $`H_\mathrm{\Delta }=\mathrm{\Delta }_i(y_i\overline{y})n_i`$ as well as the magnetic field $`B=\phi /e_0`$ perpendicular to the planar system entering the hopping $`\stackrel{~}{t}_{ij}\stackrel{~}{t}_{ij}\mathrm{exp}[i\phi y_i(x_ix_j)]`$, we can express $`R_H`$ in terms of derivatives of the ground state $`E^0(\theta ,\mathrm{\Delta },\phi )`$ with respect to external fields ,

$$R_H=\frac{NE_{\theta \mathrm{\Delta }\phi }^0}{e_0E_{\mathrm{\Delta }\mathrm{\Delta }}^0E_{\theta \theta }^0}|_{\mathrm{\Delta }=\varphi =0,\theta =\theta _0},$$
(5)
where derivatives should be taken in general at $`\theta =\theta _0`$, where $`E^0`$ is minimum.

For a reasonable application of Eq.(5), a system with $`L>M`$ is required. We therefore restrict our numerical calculations to a $`6\times 3`$ system with o.b.c. in the M direction, where a single stripe is introduced via $`H_{st}`$, Eq.(4), in the middle leg. The situation with stripe filling $`n_l=1/2`$ here corresponds to $`N_h=3`$ holes in the system. Odd $`N_h`$ has some disadvantage leading in general to $`\theta _00`$ and also to near-degenerate states at $`V=0`$. As a reference for $`V=0`$ one should expect at low doping $`n_h1/2`$ the semi-classical behavior $`R_H^{}1/e_0n_h`$, which has been in fact qualitatively reproduced using the same method . In Fig. 3 we present the results for $`R_H(n_l)`$ as they develop with the attractive potential $`V>0`$, already in the presence of small stabilizing $`h=0.1t`$. From results it is evident that for $`V0`$ Hall constant is suppressed $`|R_H|R_H^{}`$ for $`n_l=1/2`$ but as well in a wider range of stripe filling $`n_l1/2`$. On the other hand, at lowest doping $`n_h=1/N`$ we find large $`|R_H|1`$ (even changing the sign) which is an indication that the system is close to an insulator with small $`D_{xx}E_{\theta \theta }^0`$ and consequently very sensitive $`R_H`$ due to Eq.(5). Results in Fig. 4 show the effect of $`h`$ on $`R_H`$ for fixed $`n_l=1/2`$. We observe a systematic decrease of $`R_H`$ with $`h`$, and consequently $`R_H0R_H^{}`$ even at quite modest $`V/t`$.

Similar conclusions can be reached following $`D(n_l)`$ for the same $`6\times 3`$ system, as presented in Fig. 5 for $`h=0.4t`$. $`D`$ develops from quite monotonously increasing function of doping (with some finite-size even-odd effect in $`N_h`$) at $`V0,h0`$ to a dependence with a broad maximum around $`n_l1/2`$ for larger $`V`$ and $`h`$, as seen in Fig. 5, consistent with the vanishing of $`R_H`$ through Eq.(1). Such a broad maximum is also in accord with results on the $`4\times 4`$ system in Fig. 1.

Let us return in conclusion to the relevance of above results to the physics of LNSCO. Our calculations confirm that stripe structures with filling $`n_l=1/2`$ indeed have $`R_H0`$, due to a maximum $`D_{xx}`$ closely related to minimum hole kinetic energy in such configurations. Such a result should be directly relevant to the commensurate case, e.g., $`x=1/8`$ with the inter-stripe distance $`d_0=4`$ in LNSCO. In our study we however evaluate only $`R_H`$ and $`D(n_h)`$ imposing static stripes corresponding to fixed $`d_0`$ between stripes, so we can only conjecture the behavior in the regime around the commensurate values of $`x`$. Going beyond $`x>1/8`$ in LNSCO the stripes are not static (and finally disappear above the LTT-LTO transition) so our assumption of the broken symmetry is not justified any more. One can argue that the loss of the (nearly) long range stripe order leads to the situation closer to normal phase, i.e., to an increasing $`D(n_h)`$ and hence to $`R_H>0`$ approaching the behavior $`R_HR_H^{}`$ in the reference LSCO. In fact already our results in Fig. 3 indicate that $`R_H>0`$ for $`n_l>1/2`$. On the other hand, for $`x<1/8`$ experiments reveal quite static stripes with an incommensurate spin density modulation corresponding to $`d_0=2/x`$. Following our results and arguments at fixed $`d_0`$ and for the spin ordering induced by the staggered field $`h`$ we would again expect maximum $`D(n_h)`$ and consequently $`R_H0`$ at the specific stripe filling $`n_l=1/2`$. Therefore one can speculate that $`R_H0`$ persists in the whole regime of static stripes. This would be definitely a very peculiar and striking novel phenomenon, to be resolved by experiments which have so far not been performed in LNSCO well below $`x<0.12`$.

One of the authors (P.P.) acknowledges the support of the Japan Society for the Promotion of Science and the hospitality of the IMR, Tohoku University, Sendai, where this work has been initiated. The authors wish to thank also N.P. Ong, S. Uchida, J. Zaanen and X. Zotos for helpful discussions. This work has been supported in part by Grand-in-Aid for Scientific Research on Priority Areas from the Ministry of Education, Culture, Sports, Science and Technology of Japan, NEDO and CREST, and by Ministry of Science and Technology of Slovenia. The numerical calculations were performed in Supercomputer Center in ISSP, University of Tokyo, and Supercomputing facilities in IMR, Tohoku University.


text:
# Superconductivity in Dense 𝑀𝑔𝐵₂ Wires

## I Introduction

The discovery of superconductivity in $`MgB_2`$ has caused a renaissance of interest in intermetallic superconductivity. This, combined with the discovery of superconductivity in $`YPd_2B_2C`$ and the $`RNi_2B_2C`$ series several years ago,\[2-5\] seems to indicate that the old idea of looking for high intermetallic $`T_c`$ values in compounds rich in light elements is still a valid guiding principle. Measurements of the boron isotope effect in this compound are consistent with the superconductivity being mediated via electron-phonon coupling, a conclusion that is also suported by recent bandstructural calculations. Measurements of the upper critical field, $`H_{c2}(T)`$, the thermodynamic critical field, $`H_c(T)`$, and the critical current, $`J_c`$, indicate that $`MgB_2`$ is a type-II superconductor with properties that are consistent with a intermetallic superconductor that has a $`T_c40K`$. For example, other than the remarkably high $`T_c`$, $`MgB_2`$ appears to be quite similar to $`Nb_3Sn`$. Given this similarity, and given the far lower density of $`MgB_2`$ as well as the greater natural abundances of $`Mg`$ and $`B`$, a logical question is whether wires of $`MgB_2`$ can be easily synthesized, and if so what are their physical properties. In this letter we present a remarkably simple method for the synthesis of $`MgB_2`$ wires from boron filaments. In addition, we show that wires produced in this manner are of high density and have impressively low normal state resistivity and impurity scattering.

## II Experimental Methods

$`MgB_2`$ can be synthesized in powder form by reacting stoichiometric amounts of powdered $`B`$ and $`Mg`$ at 950C for approximately an hour. Given that at 950C the vapor pressure of $`Mg`$ is approximately 200 Torr, it is believed that $`MgB_2`$ forms via a process of diffusion of $`Mg`$ vapor into the boron grains. Based on this observation, the possibility of using this technique on other morphologies of boron appears to be promising.

$`MgB_2`$ wire was produced by sealing 100 $`\mu m`$ diameter boron fiber and $`Mg`$ into a $`Ta`$ tube with a nominal ratio of $`Mg_2B`$. Given that $`MgB_2`$ is the most $`Mg`$ rich binary $`MgB`$ compound known, it was felt that excess $`Mg`$ would aid in the formation of the proper, stoichiometric phase. The sealed $`Ta`$ tube was sealed in quartz and then placed into a 950C box furnace for approximately an hour. The reaction ampoule was then removed from the furnace and quenched to room temperature.

Measurement of temperature and field dependent electrical resistivity and magnetization were performed in Quantum Design MPMS and PPMS systems. Resistivity measurements were made in a standard four probe geometry using Epotek H20E silver epoxy to make contacts. The contact resistance was approximately 1 Ohm. Given the well defined geometry of the samples, accurate measurements of resistivity were possible.

## III Results

Upon opening the $`Ta`$ tube it became clear that there had been a reaction between the boron fiber and the $`Mg`$ vapor. Whereas the boron fibers were straight and moderately flexible before the reaction, the $`MgB_2`$ wires in the $`Ta`$ tube after the reaction were brittle and deformed. The inset of Figure 1 is a photograph of the resulting wires. As can be seen, there has been significant warping and bending of the fiber as a result of the reaction with the $`Mg`$ vapor. Figure 2 shows scanning electron microscope images of the fiber before the reaction as well as the wire after the reaction. In both cases a tungsten core (approximately 15 $`\mu m`$ diameter) can be clearly seen. This core is part of the original boron fiber and does not appear to be effected by the exposure of the fiber to $`Mg`$, nor, as will be seen, does it seem to effect the superconducting properties of the resulting $`MgB_2`$ wire. Whereas the boron fiber has a diameter of 100 $`\mu m`$ and breaks with a smooth, clean surface (inset to Fig. 1), the $`MgB_2`$ wire has a diameter of approximately 160 $`\mu m`$ and breaks with a rougher, grainier surface. The increased diameter of the wire is consistent with observations that there is an expansion associated with the formation of the $`MgB_2`$ powders during synthesis. Although the $`MgB_2`$ wires are somewhat brittle, the integrity of the filament segments was preserved during the exposure to the $`Mg`$ vapor, i.e. the fibers did not decompose or turn into powder.

Using a diameter of 160 $`\mu m`$ and measuring the length and mass of several wire segments we determined the density of the wire to be 2.4 $`g/cm^3`$. This is to be compared with a theoretical value of 2.55 $`g/cm^3`$ for a single crystal sample using lattice parameters $`a`$ = 3.14 $`\AA `$ and $`c`$ = 3.52 $`\AA `$ for the hexagonal unit cell. Given the rather coarse nature of our measurements, this implies that the wire samples are probably better than 80% of the theoretical density. It should be noted that the small tungsten core would come in as a roughly 10% correction, and therefore is within our level of uncertainty.

Figure 1 presents the temperature-dependent magnetization of $`MgB_2`$. The data were taken after cooling in zero field and then warming in a field of 25 Oe. Given the aspect ratio of the wire segments used we were able to obtain a susceptibility very close to $`1/4\pi `$, the value expected for total shielding and a demagnetization factor close to zero. $`T_c`$ = 39.4 K can be determined from these data by using an onset criterion (2% of $`1/4\pi `$). The width of the transition (10% - 90%) is 0.9 K.

Figure 3 presents the temperature-dependent electrical resistivity of $`MgB_2`$ wires. The room temperature resistivity has a value of 9.6 $`\mu Ohm`$-$`cm`$ whereas $`\rho (77K)`$ = 0.6 $`\mu Ohm`$-$`cm`$ and $`\rho (40K)`$ = 0.38 $`\mu Ohm`$-$`cm`$. This leads to a residual resistivity ratio of $`RRR`$ = 25.3. It should be noted that the shape of the resistivity curve and the $`RRR`$ values are qualitatively the same as those observed for sintered pellets of polycrystalline $`Mg^{10}B_2`$. The relatively low room temperature resistivity value, along with the high $`RRR`$ are not unusual for diboride samples. The resistivity of the sintered pellet samples is approximately 1 $`\mu Ohm`$-$`cm`$ at 40 K. This somewhat higher value of the calculated resistivity for the pellet is consistent with the sintered sample having an actual density substantially lower than the theoretical value.

The temperature-dependent resistivity shown in Fig. 3 can be fit by $`\rho =\rho _0+\rho _1T^\alpha `$ with $`\alpha 2.6`$ between $`T_c`$ and 200 K. This is comparable to the power law $`R=R_1+R_1T^{\alpha _1}`$ with $`\alpha _12.8`$ found for the sintered $`Mg^{10}B_2`$ sample over a comparable temperature range. Given the similarity of the two power laws it seems clear that the resistivity of $`MgB_2`$ will not have a linear slope for temperatures between $`T_c`$ and 300 K. On the other hand, using an average Fermi velocity of $`v_F=4.810^7cm/s`$ and a carrier density of $`6.710^{22}el/cm^3`$ (two free electrons per unit cell) we can estimate the electronic mean free path to be approximately 600 $`\AA `$ at $`T_c`$. This is clearly an approximate value of the electronic mean free path, but given the estimated superconducting coherence length of approximately 50 $`\AA `$, these values place $`MgB_2`$ wires well within the clean limit. Given a $`\kappa 26`$, this implies that, much like the case of the $`RNi_2B_2C`$ materials, there may be significant non-local effects associated with $`MgB_2`$.

The superconducting transition temperature, $`T_c`$ = 39.4 K, can be determined from both the magnetization and resistivity data shown in Figs. 1 and 3. This value is slightly higher than the $`T_c`$ = 39.2 K value determined for isotopically pure $`Mg^{11}B_2`$, but is significantly lower that $`T_c`$ = 40.2 K for $`Mg^{10}B_2`$. This is consistent with an approximate 80 % natural abundance of $`{}_{}{}^{11}B`$. It is noteworthy that the superconducting transition is both relatively high and sharp in the wire samples. This means that either very few impurities are being incorporated into the $`MgB_2`$ or that what few impurities are being incorporated are having very little effect on either resistivity or $`T_c`$.

The temperature dependence of the upper critical field, $`H_{c2}(T)`$, is shown in the inset to Fig. 3. For each field three data points are shown: onset temperature, temperature for maximum $`d\rho /dT`$, and completion temperature. Qualitatively these data are remarkably similar to the $`H_{c2}(T)`$ data inferred from measurements on $`Mg^{10}B_2`$ sintered pellets as well as recent measurements on hot-pressed powders. Quantitatively, at $`H`$ = 9 T, the width of the resistive transition for the wire sample is roughly half of the width found for the sintered sample. These data are consistent with the wire sample being of comparable or better quality as the sintered powder samples.

Figure 4 presents data on the critical current $`J_c`$. The open symbols are $`J_c`$ values extracted from direct measurements of the current dependent voltage across the sample at given temperature and applied field values. The filled symbols are $`J_c`$ values inferred from magnetization loops by application of the Bean model. The direct measurement of $`J_c`$ was limited to values below approximately 200 $`A/cm^2`$ due to resistive heating from the sample leads and contact resistance. As can be seen, the extrapolations of the directly measured, low $`J_c`$, data and the Bean-model-inferred, high $`J_c`$, data match up moderately well. In comparison to the $`J_c`$ data presented for a sintered pellet of $`Mg^{10}B_2`$, $`J_c`$ for the wire sample is roughly a factor of two higher at low fields and temperatures and over an order of magnitude higher at high fields.

## IV Conclusions

We have devised a simple technique of producing low resistivity, high density, high $`T_c`$ $`MgB_2`$ in wire form via exposure of boron filaments to $`M`$g vapor. The resulting wire has better than 80% the theoretical density of $`MgB_2`$ and measurements of the temperature dependent resistivity reveal that $`MgB_2`$ is highly conducting in the normal state. The room temperature resistivity has a value of 9.6 $`\mu Ohm`$-$`cm`$ whereas the resistivity at $`T`$ = 40 K is 0.38 $`\mu Ohm`$-$`cm`$. This means that even in the normal state wires of $`MgB_2`$ can carry significant current densities. This should be compared with the resistivity of $`Nb_3Sn`$ $`\rho (20K)`$ = 11 $`\mu Ohm`$-$`cm`$ and $`\rho (300K)`$ = 80 $`\mu Ohm`$-$`cm`$.

Given the well-defined geometry of the wire samples we have been able to directly measure a full $`1/4\pi `$ susceptibility in the superconducting state. The values of $`T_c`$ for this wire sample are slightly higher than the $`T_c`$ values for isotopically pure $`Mg^{11}B_2`$ sintered powders and the width of the resistive superconducting transition is smaller that that seen for $`Mg^{10}B_2`$ sintered powders. In addition, $`H_{c2}(T)`$ for the wire sample is virtually the same as that found for $`Mg^{10}B_2`$ sintered pellets. Based on all of these observations it appears that $`MgB_2`$ wires provide dense, high quality samples of $`MgB_2`$. By comparing our estimate of the electronic mean free path $`l600\AA `$ to the superconducting coherence length $`\xi 50\AA `$ we can see that $`MgB_2`$ wires are well within the clean limit.

All of the above, of course, presents the possibilities of using such wires for both research and applied purposes. For basic research the possibilities of making weak link Josephson junctions, SLUGS, and other devices are currently being pursued. On the applied side, given that boron filaments are produced in a variety of sizes and of arbitrary lengths, the possibility of converting boron filament into $`MgB_2`$ wire as part of a continuous process leads to the possibility of simple manufacturing of light weight, high $`T_c`$, wires with remarkably small normal state resistivities. In addition, this process could be used to turn boron coatings on tapes, cavities, or other devices into high-quality superconducting films. Although the low temperature $`J_c`$ values are currently smaller than those for $`Nb_3Sn`$, as of yet very little effort has been put into optimizing $`J_c`$. A multi-dimensional phase space of filament purity, diameter, treatment time and temperature has yet to be explored. Both basic and applied directions of research will have to be explored in detail over the coming months and years.

## V Acknowledgments

We would like to thank V. Crist and M. Kramer for taking the electron microscope images as well as J. R. Clem and R. W. McCallum for useful discussions and N. Anderson and N. Kelso for assistance in the lab. Ames Laboratory is operated for the U. S. Department of Energy by Iowa State University under Contract No. W-7405-Eng.-82. This work was supported by the director fo Energy Research, Office of Basic Energy Sciences.