format: text

text:
# ROTATIONAL AND VIBRATIONAL DYNAMICS OF INTERSTITIAL MOLECULAR HYDROGEN

## I INTRODUCTION

The study of rotational and vibrational dynamics of guest molecules (i.e. CO, O2, H2, etc) trapped in porous media such as fullerenes, zeolites, and graphite has recently become an active subject both experimentally and theoretically. This is because such studies can yield valuable information about the host-guest interactions which could be important for several technical applications such as gas separation and hydrogen storage. In particular hydrogen molecules trapped in interstitial cavities in solid C60 as well as hydrogen molecules embedded in nanotube ropes are of interest due to quantum behavior of hydrogen molecules in quasi zero and one dimensional sites.

In this paper, we develop a detailed analysis of coupled rotational and vibrational dynamics of a molecular hydrogen encapsulated in a solid using numerical, perturbative, and group theoretical methods. In particular we will be interested in what one might call the “weak coupling limit,” when the interaction between molecular rotations and center-of-mass translations is weak enough that the rotational angular momentum quantum number $`J`$ is a good quantum number. This limit is almost never satisfied except for very light molecules like hydrogen or deuterium. The energy levels of a free rotator are

$`E_J=BJ(J+1),`$ (1)
where $`B=\mathrm{}^2/(2I)`$, where $`I`$ is the moment of inertia of the molecule and $`E_J`$ is $`(2J+1)`$-fold degenerate. For H2 the rotational constant $`2B`$ has the value $`60`$ cm-1, 14.7 meV, or $`B/k=85`$ K (and the corresponding values for D2 are half as large), so that the energy separation between different $`J`$ levels is large enough that often $`J`$ is a good quantum number. This is certainly true for solids consisting of these molecules unless the pressure is quite large. (For a review of the properties of the hydrogen molecule and solid hydrogen see Ref. .)

We have been led to consider this phenomenon in view of an experimental study of energy spectra of H2 and D2 inserted into the octahedral interstitial sites in solid C60 carried out by neutron time of flight techniques. In considering this phenomenon we should keep in mind the following experimental facts concerning the host solid of C60. The centers of the C60 molecules form an fcc lattice. At temperature above $`T_c`$, where $`T_c`$ is about 260 K, the molecules are orientationally disordered. At $`T=T_c`$ long range orientational ordering occurs and the molecules are ordered into four sublattices as described by Pa$`\overline{3}`$ symmetry. In the orientationally disordered phase the local symmetry at the the octahedral interstitial site is indeed that of the point group Oh. In the presence of orientational ordering the symmetry of what was the “octahedral” interstitial site is now reduced to a uniaxial symmetry, specifically that of point group S6. In experiments, hydrogen molecules are stable in the octahedral interstitial site only for temperatures well below $`T_c`$ (where the interstitial site does not actually have octahedral symmetry).

While a general understanding of the time-of-flight experiments was presented, some of the finer details of the experiment remained unexplained. For instance, the shift in the energy associated with ortho-para ($`J=1J=0`$) conversion in the interstitial relative to its value for free molecules was not understood. Also the feature in the energy gain spectrum at about twice the ortho-para conversion energy was not unambiguously identified. These issues are both addressed in this paper. More generally we give a calculation of the cross section for neutron energy loss for comparison with the observed time-of-flight spectrum. For that purpose we need not only to consider the cross section for para-ortho conversion as compared to phonon creation, but also to calculate the phonon excitations of $`(J=1)`$ molecules. These calculations require us to develop and implement a scheme for treating coupled translations and rotations. In this paper we present a systematic analysis of the simplest case of this coupling which occurs when the quantum number $`J`$ characterizing free rotation remains a good quantum number. In that case the well-known numerical schemes for solving the translation problem can be easily extended to include the effect of the coupling to rotations. In addition, we also give analytic expressions obtained by treating this coupling within perturbation theory. As we will see, this analytic development enables us to interpret many of the numerical results in a meaningful way. In addition, we analyze in detail various simplified models which illustrate our group theoretical analysis of the symmetry present in the system of coupled translations and rotations. This analysis indicates that arguments for the degeneracies of coupled translation-rotation modes based on simple classical concepts are incorrect. In summary: in this paper we present an analysis based on numerical, perturbative, and group theoretical methods.

Up to now there have not been many theoretical studies of energy levels in such irregular geometries like the octahedral interstitial sites in C60. A notable exception is the work of van der Avoird and collaborators on CO in C60. That work examined an even more complicated situation in which the rotational and translation degrees of freedom interacted strongly. As a result, the problem was analyzed numerically. In contrast, for the present problem FitzGerald et al. applied a number of analytic and semi-analytic techniques to the theoretical study the spectra of hydrogen molecules in C60. This paper may be regarded as an extension and systematization of their approach.

## II GENERAL FORMULATION

Clearly the first step is to establish a satisfactory potential for the intercalated hydrogen molecule. This potential function $`V(𝐫,\mathrm{\Omega })`$ gives the energy of a hydrogen molecule whose center of mass is at $`𝐫`$ and whose orientation is specified by $`\mathrm{\Omega }(\theta ,\varphi )`$. A convenient starting point is to use an atom-atom potential to describe the interaction between each of the two hydrogen atoms and the atoms in the confining structure. Unless otherwise indicated, all the results reported in this paper are obtained from the same WS77 potential, $`A/r^6+B\mathrm{exp}(Cr)`$, that is used in Ref. (where $`A=5.94\mathrm{eV}\AA ^6,B=678.2`$ eV, and $`C=3.67\AA ^1`$).

In this paper we will mainly consider the octahedral interstitial site in solid C60, but many of the considerations apply with slight modification to molecules confined within other structures such as single wall carbon nanotubes. The determination of the potential $`V(𝐫,\mathrm{\Omega })`$ for H2 in solid C60 is discussed in Appendix A. From the numerical evaluation of this potential we have extracted the expansion coefficients when it is written in the following canonical form:

$`V(𝐫,\mathrm{\Omega })=V_0(𝐫)+{\displaystyle \underset{l=2,4,\mathrm{}}{}}{\displaystyle \underset{m=l}{\overset{l}{}}}A_l^m(𝐫)Y_l^m(\mathrm{\Omega }).`$ (2)
We assume (and it is generally true) that the orientational energies which are relevant are much less than the smallest energy difference between successive $`J`$ levels of a molecule ($`10B`$ for an ortho molecule and $`6B`$ for a para molecule). Accordingly, we may consider only that part of the potential which is diagonal in $`J`$. When the potential is written in the form of Eq. (2), it is easy to implement the truncation to terms diagonal in $`J`$. So for a fixed value of $`J`$ we have the Hamiltonian $`_J`$ as

$`_J`$ $`=`$ $`{\displaystyle \frac{p^2}{2m}}+V_0(𝐫)+BJ(J+1)+{\displaystyle \underset{l=2,4,\mathrm{}}{}}{\displaystyle \underset{\mu ,\mu ^{}}{}}A_l^{\mu \mu ^{}}(𝐫)\left[|J\mu J\mu |Y_l^{\mu \mu ^{}}(\mathrm{\Omega })|J\mu ^{}J\mu ^{}|\right]`$ (3)
$`=`$ $`{\displaystyle \frac{\mathrm{}^2}{2m}}^2+V_0(𝐫)+BJ(J+1)+V_J(𝐫),`$ (4)
where $`V_J(𝐫)`$ is the orientationally dependent part of the potential (the terms involving $`A_l^m`$) and $``$ is the unit operator. Furthermore we consider the angular-dependent term in this expansion to be a perturbation on the first term, $`V_0(𝐫)`$. For each value of $`J`$ the Hamiltonian $`_J`$ will give a manifold of states which is the direct product of a manifold corresponding to various numbers of localized phonons being excited with the manifold of $`(2J+1)`$ states having different values of $`m_J`$. An important simplification is that spherical harmonics with $`l>2J`$ have no nonzero matrix elements in the manifold of states of angular momentum $`J`$.

Note that apart from the kinetic energy, this Hamiltonian is a strictly local operator. Thus we solve the eigenvalue problem on a discrete mesh of points on a cube centered at the octahedral site when the wave function is required to vanish on the boundary of the cube. Each edge of the cube is taken to be $`[L,L]`$ with mesh point spacing of $`dL`$. In this scheme the wave function at each mesh point is a $`(2J+1)`$-component vector. We are mainly concerned with the manifold $`J=0`$ and $`J=1`$, in which case the problem is numerically not significantly harder than for a scalar problem. Even though the resulting matrix size is very large, it is a block band matrix and is very sparse. The numerical results reported here were obtained from L=1.65 Å and $`dL=0.075`$ Å, which requires diagonalization of a matrix $`n\times n`$ where $`n=273375`$). However we confirmed that a coarse mesh points with $`L=1.2`$ Å and $`dL=0.17`$ Å, gives almost the same results (where the matrix size is $`n=14,739`$). The large sparse matrix eigenvalue problem is solved using the package ARPACK.

Since numerical results sometimes do not provide complete insight into the nature of the solutions, we have also used perturbation theory to understand the results. In this approach we treat $`V_J(𝐫)`$ in Eq. (4) as the perturbation. The unperturbed problem, apart from the additive energy $`BJ(J+1)`$ is thus that for translations of the spherical $`(J=0)`$ molecule. This spectrum is not too different from that of a three-dimensional harmonic oscillator. Accordingly, to qualitatively interpret our more accurate numerical results, we apply perturbation theory in which we develop an effective Hamiltonian to describe the splitting of this manifold which is characterized by a value of $`J`$ and of $`N`$, the total number of phonon excitations. (The perturbative effects due to coupling between manifolds of different $`J`$ is negligibly small for hydrogen in C60.) This effective Hamiltonian is a matrix of dimensionality $`D`$, where $`D=(2J+1)(N+1)(N+2)/2`$ and schematically is of the form

$`(N,J)`$ $`=`$ $`BJ(J+1)+_{\mathrm{phonon}}+V_J^{\mathrm{DIAG}}V_J^{\mathrm{OFF}}{\displaystyle \frac{1}{}}V_J^{\mathrm{OFF}},`$ (5)
where $`_{\mathrm{phonon}}`$ gives the energy of the various states with a total of $`N`$ phonons. These energies are just those calculated for a $`(J=0)`$ molecule. Also $`V_J^{\mathrm{DIAG}}`$ is the part of $`V_J`$ which is diagonal with respect to the number of phonons, $`V_J^{\mathrm{OFF}}`$ is the part of $`V_J`$ which is off-diagonal with respect to the number of phonons, and $``$ is the change in phonon energy caused by $`V_J^{\mathrm{OFF}}`$.

This effective Hamiltonian is defined by its matrix elements as

$`N,\alpha `$ ; $`J,M|(J,N)|N,\alpha ^{};J,M^{}=[BJ(J+1)+E_{N,\alpha }]\delta _{\alpha ,\alpha ^{}}\delta _{M,M^{}}`$ (9)
$`+{\displaystyle \underset{l=1}{\overset{J}{}}}N,\alpha |A_{2l}^{MM^{}}(𝐫)|N,\alpha ^{}JM|Y_{2l}^{MM^{}}(\mathrm{\Omega })|JM^{}`$
$`+{\displaystyle \underset{N^{}N}{}}{\displaystyle \underset{l,l^{}=1}{\overset{J}{}}}{\displaystyle \underset{\mu }{}}{\displaystyle \underset{\beta =1}{\overset{k_N^{}}{}}}[E_{N,\alpha }E_{N^{},\beta }]^1N,\alpha |A_{2l}^{M\mu }(𝐫)|N^{},\beta N^{},\beta |A_{2l^{}}^{\mu M^{}}(𝐫)|N,\alpha ^{}`$
$`JM|Y_{2l}^{M\mu }(\mathrm{\Omega })|J\mu J\mu |Y_{2l^{}}^{\mu M^{}}(\mathrm{\Omega })|JM^{},`$
where $`k_N=(N+1)(N+2)/2`$ and the states with $`N`$ phonons are labeled $`N,\alpha `$, where $`\alpha `$ runs from 1 to $`k_N`$.

We now briefly discuss how the $`A_l^m`$’s of Eq. (2) are obtained from the atom-atom potential between each H atom and each carbon atom. Here we will assume that the atom-atom potential is of the form $`F(|𝐫_i𝐫_H|)`$, where $`𝐫_i`$ and $`𝐫_H`$ are the displacements of the $`i`$th carbon and of the H atom, respectively, relative to the center of the H2 molecule. For this form of potential, we show in Appendix A that

$`A_2^m`$ $`=`$ $`2\pi {\displaystyle \underset{i}{}}Y_2^m(\widehat{𝐫}_i)^{}{\displaystyle _1^1}(3x^21)F\left([r_i^2{\displaystyle \frac{1}{/}}4\rho ^2+\rho xr_i]^{1/2}\right)𝑑x,`$ (10)
where $`\rho `$ is the separation between H atoms in the H2 molecule and the sum over $`i`$ is over all relevant neighboring carbon atoms. It is instructive to expand this expression in $`\rho /r_i`$, which yields

$$A_2^m=\frac{1}{4}\rho ^2\left(\frac{8\pi }{15}\right)\underset{i}{}\left(F^{^{\prime \prime }}\frac{F^{^{}}}{r_i}\right)Y_2^m(\widehat{𝐫}_i)+o(\rho ^4/r_i^4),$$
(11)
where $`F^{^{\prime \prime }}`$ and $`F^{^{}}`$ are the second and first derivatives of $`F(r_i)`$.

This expansion is good enough to reproduce most of the results discussed in this paper. We note that the $`A_l^m`$’s (i.e. the orientational potential) are zero for a harmonic potential (i.e. $`F(r_i)=\frac{1}{2}kr_i^2`$) because the prefactor $`(F^{^{\prime \prime }}F^{^{}}/r_i)`$ is zero. This can be also seen easily as follows. Assuming an atom-atom potential between each H atom and the C atoms in the adjacent C60 molecules, we may write the potential of an H2 molecule as

$`V(𝐫;\mathrm{\Omega })`$ $`=`$ $`V_a(𝐫+{\displaystyle \frac{1}{/}}2\rho \widehat{n})+V_a(𝐫{\displaystyle \frac{1}{/}}2\rho \widehat{n}),`$ (12)
where $`V_a`$ is the potential of a single atom due to the entire octahedral cage in which it is confined, $`\widehat{n}`$ is a unit vector along the axis of the molecule, and $`\rho `$ is the separation between atoms in the molecule. As we shall see, the total potential is nearly isotropic. So we write

$`V_a(𝐫)`$ $`=`$ $`{\displaystyle \frac{1}{/}}2kr^2+\delta r^4.`$ (13)
When we substitute this into Eq. (12), we obtain the result

$`V(𝐫;\mathrm{\Omega })`$ $`=`$ $`V_0(r)+2\delta [r^2\rho ^2\mathrm{cos}^2\theta _{r,n}{\displaystyle \frac{1}{/}}3],`$ (14)
where $`\theta _{r,n}`$ is the angle between the vectors $`𝐫`$ and $`\widehat{n}`$ and $`V_0`$ is independent of $`\theta _{r,n}`$. The point is that the orientationally dependent part of the interaction depends on the anharmonicity: for a purely harmonic and isotropic interaction $`V_a`$, the total potential energy is independent of the molecular orientation. Thus we expect rotation-translation coupling to be weak. On the other hand in nanotubes, where the quadratic term is anisotropic, this coupling will be more important.

## III ENERGY SPECTRUM OF A $`(J=0)`$ H2 MOLECULE

We start by considering the eigenvalue spectrum of $`_0`$ in which the orientational dependence of the potential is neglected. In this approximation, apart from the additive constant $`BJ(J+1)`$, the total energy (rotational plus translational) is the same as that of a $`(J=0)`$ molecule. For most purposes a $`(J=0)`$ molecule may be considered to be a spherical molecule because the orientational wave function $`Y_0^0(\mathrm{\Omega })`$ is uniform over all orientations. Each eigenfunction of $`_0(J)`$ is the product of a rotational function taken from the manifold of $`2J+1`$ degenerate orientational wave functions and a translational wave function which represents an eigenfunction for a spherical molecule confined to a cage. These translational wave functions satisfy

$`_0\psi _k(𝐫)=\left[{\displaystyle \frac{p^2}{2m}}+V_0(𝐫)\right]\psi _k(𝐫)=E_k\psi _k(𝐫),`$ (15)
where $`V_0(𝐫)`$ is the potential discussed in Appendix A. The index $`k`$ labels states which we might otherwise label by three indices, each quantum number characterizing the number of excitations in each direction. Note that these unperturbed solutions do not involve the coupling between rotations and translations. As discussed above, these eigenfunctions were obtained by converting the continuum equation (15) into a into a discrete equation on a mesh of points and solving the resulting matrix eigenvalue problem using a sparse matrix routine.

Since it happens that the energy levels and eigenfunctions we obtained numerically are not qualitatively different from those of a spherical harmonic oscillator, we first study the energy spectrum as perturbations, $`\delta ,\kappa `$, and $`\lambda `$, are sequentially turned on in the following potential:

$$V(r)=\frac{1}{2}kr^2+\delta r^4+\kappa (x^4+y^4+z^4\frac{3}{/}5r^4)+\lambda (xy+yz+zx).$$
(16)
Fig. 1 shows the evolution of the energy spectrum as perturbations are sequentially introduced which take the spherical harmonic oscillator into the actual lower symmetry of a molecule in an octahedral interstitial site. In the left-most panel we show the energy levels for a spherical harmonic oscillator, with $`\mathrm{}\omega `$ adjusted to correspond to the single-phonon levels of H2 in an octahedral interstitial site in C60. Note that the levels are highly degenerate because the energy depends only on the total number of quanta. The symmetry of the Hamiltonian is $`U(3)`$, the group of unitary three dimensional matrices. We now add to this potential an anharmonic term of the form $`\delta r^4`$. This perturbation lowers the symmetry to that of the rotation group in three dimensions. As is well known, each eigenfunction in a generic spherically symmetric potential can be labeled by the magnitude of the orbital angular momentum, $`L`$. Thus the single phonon levels are unsplit by this anharmonic perturbation and are now labeled as angular momentum $`L=1`$ states, whereas the two phonon levels split into a manifold of five $`L=2`$ states and one $`L=0`$ state and similarly for states with more than two phonons. In Fig. 1 we have taken the constant $`\delta `$ to be that which best describes the anharmonicity of H2 in C60. The energies of the perturbed levels are given in Table I.

Next, we consider what happens when the spherical oscillator potential is augmented by a cubic symmetry potential of the form $`\kappa (x^4+y^4+z^4\frac{3}{/}5r^4)`$. This potential is appropriate for a spherical molecule in an octahedral interstitial when the C60 are orientationally disordered and have an Fm3m crystal structure. The degeneracy associated with spherical symmetry is lifted, but as shown here one retains cubic symmetry, so the three one-phonon states which transform as $`x`$, $`y`$, and $`z`$ are degenerate. The two-phonon states are of three different symmetries. One ($`t_{2g}`$) transforms like $`xy`$, $`xz`$, and $`yz`$. This is the lowest level. The next highest level is the s-wave symmetric combination which transforms like $`x^2+y^2+z^2`$. Then one has a doublet of d-wave ($`e_{2g}`$) symmetry. This classification scheme is continued in the higher-energy levels. Although we are not dealing with harmonic phonons, it is still useful to consider manifolds characterized by the quantum numbers $`J`$ and $`N`$, which are respectively the rotational angular momentum and the total number of phonons, at least up to $`N=3`$. Quantitative results are given in Table II.

Finally, in the rightmost panel of Fig. 1 we show the further reduction in degeneracy which occurs when the octahedral interstitial is surrounded by C60 molecules which have the long range order associated with the Pa$`\overline{3}`$ crystal structure. In this case, each interstitial is uniaxial (with symmetry S6) rather than octahedral. Accordingly, we introduce a potential of the form $`\lambda (xy+yz+zx)\frac{1}{/}2\lambda (3\xi ^2r^2)`$, where the $`\xi `$ axis is taken to lie along the three-fold axis of the interstitial site. There are four symmetry related interstitial sites, each of which has its three-fold axis along a different $`[1,1,1]`$ direction. The resolution of degeneracy in the presence of this uniaxial perturbation is also given in Table II. In all these cases, no interactions between rotations and translations are involved.

We have solved the eigenvalue problem of Eq. (15) on a mesh of points and obtained the results given in Table III. Results labeled ”Octahedral” are those for the orientationally disordered phase, where each C60 molecule is replaced by a sphere of carbon atoms as is discussed in Ref. . Since these numerical results lead to manifolds of energy levels associated with a given number of phonons and the degeneracies of these manifolds are as expected from our general discussion above, we conclude that the potential seen by a spherical H2 molecule in the low-lying phonon levels is not very different from that of a spherical harmonic oscillator. However as noted in Ref., the effective harmonic potential must be taken to be a self-consistently renormalized potential to take account of the larger zero-point motion.

## IV ENERGY SPECTRUM OF A $`J=1`$ MOLECULE

We now discuss the energy spectrum of an ortho molecule with $`(J=1)`$. As we have seen for $`(J=0)`$ molecules, our numerical results indicate that for $`N`$ up to, say, three, one can clearly identify the manifold of $`N`$ phonons. We therefore discuss the systematics of these manifolds.

### A Zero-Phonon Manifold

We first consider the case of $`J=1`$ with $`N=0`$ phonons. This manifold is described by the effective Hamiltonian

$``$ $`=`$ $`[2B+\mathrm{\Delta }E]+\delta [J_z^2{\displaystyle \frac{2}{/}}3].`$ (17)
The splitting $`\delta `$ must be zero when C60 is orientationally disordered. From Eq. (9) one sees that because the spherical harmonics are traceless, the average energy shift, $`\mathrm{\Delta }E`$, has nonzero contributions only from terms which involve coupling to excited phonon states. (In Ref.  a negligibly small shift was found due to effects off-diagonal in $`J`$ which we ignore here.) From Eq. (9) we find that

$`\mathrm{\Delta }E`$ $`=`$ $`{\displaystyle \frac{1}{/}}3{\displaystyle \underset{N0,\alpha }{}}E_{N,\alpha }^1{\displaystyle \underset{\mu ,\tau }{}}|0,1|A_2^\tau (𝐫)|N,\alpha |^2|1(\mu +\tau )|Y_2^\tau (\mathrm{\Omega })|1\mu |^2.`$ (18)
To implement this equation, we first construct $`A_l^m(𝐫)`$ as discussed in Eq. (10). Then matrix elements of $`A_2^M(𝐫)`$ are taken between phonon states for a $`J=0`$ molecule which we obtained previously and which are labeled $`N,\alpha `$ ($`|0,1`$ being the phonon ground state). Thereby we obtained the results given in Tables IV and V. In Eq. (18) the matrix elements of spherical harmonics $`Y_2^M(\mathrm{\Omega })`$ are taken between orientational states labeled by $`J`$ and $`J_z`$. To evaluate $`\mathrm{\Delta }E`$ we use

$`{\displaystyle \underset{\mu }{}}|1(\mu +\tau )|Y_2^\tau (\mathrm{\Omega })|1\mu |^2={\displaystyle \frac{3}{10\pi }}`$ (19)
so that

$`\mathrm{\Delta }E`$ $`=`$ $`{\displaystyle \frac{1}{10\pi }}{\displaystyle \underset{N0,\alpha }{}}E_{N,\alpha }^1{\displaystyle \underset{\tau }{}}|0,1|A_2^\tau (𝐫)|N,\alpha |^2.`$ (20)
In appendix B we give a model calculation of an H2 molecule in a spherical cavity from which we evaluate Eq. (20) to give $`\mathrm{\Delta }E=0.14\mathrm{meV}`$. In this calculation the translational wave functions are assumed to be those of a harmonic oscillator with $`r^2=0.1875\AA ^2`$. As noted, the result is very sensitive to the value used for $`r^2`$. For octahedral symmetry (i. e. for orientationally disordered C60) we evaluate Eq. (20) using the data in Table IV. Thereby we find a shift $`\mathrm{\Delta }E=0.133`$ meV. The same approach using our numerical solutions for the phonon states of a $`(J=0)`$ molecule for the orientationally ordered Pa$`\overline{3}`$ phase yields the result, $`\mathrm{\Delta }E=0.141\mathrm{meV}`$, compared to the experimental value $`\mathrm{\Delta }E=0.35`$ meV. Again we mention that a small change in parameters could easily lead to a much larger calculated value of $`\mathrm{\Delta }E`$. From the numerical solution for the three component wave function of a $`(J=1)`$ molecule on a mesh of points, we obtained the value $`\mathrm{\Delta }E=0.16`$ for the Pa$`\overline{3}`$ phase. The various numerical results for $`\mathrm{\Delta }E`$ are summarized in Table VI.

From Eq. (9) we also find the splitting (in the Pa$`\overline{3}`$ phase) to be

$`\delta `$ $`=`$ $`{\displaystyle \frac{30,1|A_2^0|0,1}{\sqrt{20\pi }}}`$ (22)
$`+{\displaystyle \frac{3}{20\pi }}{\displaystyle \underset{e}{}}E(e)^1\left[|0,1|A_2^0(𝐫)|e|^2+|0,1|A_2^1(𝐫)|e|^22|0,1|A_2^2(𝐫)|e|^2\right],`$
where the quantization axis is taken to lie along the threefold axis of symmetry of the interstitial site. Using the matrix elements given in Table IV, we find that the contribution to the splitting $`\delta `$ comes almost exclusively from the diagonal term $`0,1|A_2^0|0,1`$ and we obtain the results listed in Table VI.

### B One-Phonon Manifold

#### 1 Numerical Results

Next we consider the manifold $`J=1`$ with $`N=1`$ phonon. Again only $`Y_l^m`$ with $`l=2`$ contributes, so that we may write

$`(1,1)_{\alpha \mu ;\alpha ^{}\mu ^{}}`$ $``$ $`\alpha \mu |(N=1,J=1)|\alpha ^{}\mu ^{}`$ (23)
$`=`$ $`[2B+E_0+\mathrm{}\omega _\alpha ]\delta _{\mu ,\mu ^{}}\delta _{\alpha ,\alpha ^{}}+1\alpha |A_2^{\mu \mu ^{}}(𝐫)|1\alpha ^{}1\mu |Y_2^{\mu \mu ^{}}(\mathrm{\Omega })|1\mu ^{}`$ (26)
$`{\displaystyle \underset{N^{}1}{}}{\displaystyle \underset{\alpha ^{\prime \prime }=1}{\overset{k_N^{}}{}}}{\displaystyle \underset{\mu ^{\prime \prime }}{}}{\displaystyle \frac{1}{E_{N^{},\alpha ^{\prime \prime }}E_{1,\alpha }}}1\alpha |A_2^{\mu \mu ^{\prime \prime }}(𝐫)|N^{}\alpha ^{\prime \prime }N^{}\alpha ^{\prime \prime }|A_2^{\mu ^{\prime \prime }\mu ^{}}(𝐫)|1\alpha ^{}`$
$`\times 1\mu |Y_2^{\mu \mu ^{\prime \prime }}(\mathrm{\Omega })|1\mu ^{\prime \prime }1\mu ^{\prime \prime }|Y_2^{\mu ^{\prime \prime }\mu ^{}}(\mathrm{\Omega })|1\mu ^{}.`$
This is a $`9\times 9`$ matrix, which gives the 9 ($`J=1,N=1`$) levels. Since the first term gives rise to the removal of degeneracy expected from group theoretical considerations, we did not include the second term in our numerical evaluations. This procedure was sufficiently accurate to provide a useful check on the validity of the more accurate numerical solutions for the three-component wave functions of our set of mesh points. In Table VII these numerical results (“full mesh”) are given and are compared to the results using perturbation theory, as in Eq. (26). As can be seen, the two approaches yield quite compatible results.

#### 2 Qualitative Remarks

Some additional comments on Eq. (26) are in order. The first line of this equation gives the energy at first order in perturbation theory. At this order the wave function remains a product of the spatial ground-state spatial wave function for a $`J=0`$ molecule times a $`J=1`$ rotational wave function. At this level of approximation there is no dynamical coupling between translation and rotation. In second order perturbation theory we see that admixtures of two phonon states which are multiplied by different rotational states are introduced. For example, consider the situation when the molecule is in a uniaxial symmetry site and let $`|X`$, $`|Y`$, and $`|Z`$ be the $`J=1`$ states for which respectively $`J_x`$, $`J_y`$, and $`J_z`$ are zero. If, for simplicity, we assume that the unperturbed spatial wave function is spherically symmetric, then the state which without perturbation was

$`C_0|Ze^{r^2/(4\sigma ^2)}`$ (27)
where $`C_0`$ is a normalization constant, is now

$`C_1|Ze^{r^2/4\sigma ^2}+C_2|Xzxe^{r^2/(4\sigma ^2)}+C_2|Yzye^{r^2/(4\sigma ^2)},`$ (28)
where $`C_1C_0`$ and $`C_2`$ is small compared to $`C_1`$. The point is that this formulation allows the molecule to change its orientational state as it translates. For H2 in C60 this effect is small, however, in less symmetrical cavities, as in nanotubes, this effect can become more important.

#### 3 Group Theoretical Analysis

In Fig. 2 we show the influence of roton-phonon coupling and local site symmetry on the energy spectrum of the one phonon-$`(J=1)`$ manifold. At the far left we start from the case of highest symmetry when the phonon and rotations separately have complete rotational invariance and no phonon-roton coupling is present. In this case the manifold of 9 states (3 one-phonon states $``$ 3 $`(J=1)`$ states) is completely degenerate. When roton-phonon coupling is included (but the environment is still spherically symmetric) we have overall rotational invariance and the resulting eigenstates are characterized by their total angular momentum $`K`$. The roton-phonon coupling causes states with different $`K`$ to have different energy. (The size of the splitting shown in the figure is adjusted to agree with the center of gravity of the appropriate levels for cubic site symmetry.)

The two right-hand columns pertain to the situation when a $`(J=1)`$ hydrogen molecule occupies the octahedral interstitial site of C60. When the C60 molecules are orientationally disordered the interstitial site has Oh symmetry and we consider that case first. Use of the character tables for the Oh group indicates that the original 9 dimensional reducible representation $`\mathrm{\Gamma }`$ is decomposed into irreducible representation of the Oh group as

$`\mathrm{\Gamma }`$ $`=`$ $`T_{2\mathrm{g}}T_{1\mathrm{g}}E_\mathrm{g}A_\mathrm{g}.`$ (29)
and the basis functions associated with these irreducible representations are given in Table VIII. As mentioned above, for temperatures below about 260K, the C60 molecules order into a structure of crystal symmetry Pa$`\overline{3}`$ in which case the formerly octahedral interstitial has the lower S6 symmetry. Use of the relevant character table shows that now

$`\mathrm{\Gamma }`$ $`=`$ $`3A_\mathrm{g}3E_\mathrm{g}3E_\mathrm{g}^{},`$ (30)
where $`E_g`$ is a complex one dimensional representation and $`E_g^{}`$ is its complex conjugate partner. The basis functions associated with these irreducible representations are given in Table VIII. The most important conclusion from this analysis is that the energy eigenfunctions are not simply products of translational and rotation wave functions, but instead are linear combinations of such products. This type of wavefunction reflects the fact that symmetry operations act simultaneously on the position and the orientation of a molecule.

To emphasize this fact we give, in Fig. 3, a pictorial representations of the translation-rotation wavefunctions. This representation is to be interpreted as follows. We know that the rotational wave functions for a free $`J=1`$ molecule can be taken to be analogs of $`p_x`$, $`p_y`$ and $`p_z`$ functions and we will label these rotational wavefunctions as $`X`$, $`Y`$, or $`Z`$. For instance $`|X\mathrm{sin}\theta \mathrm{cos}\varphi `$, $`|Y\mathrm{sin}\theta \mathrm{sin}\varphi `$, and $`|Z\mathrm{cos}\theta `$. These wave functions have two lobes, one positive the other negative aligned along the axis associated with their state label. When such a rotational function is multiplied by a one phonon function in the $`\alpha `$ direction, ($`|x`$ denotes a wave function for a single phonon excitation in the $`x`$-direction), the total wave function will be an odd function of $`\alpha `$. Thus the wave function $`|xX`$ is an odd function of $`x`$ and is therefore depicted by two $`p_x`$ functions, one at positive $`x`$ and another at $`x`$ with the signs of the two lobes changed. For simplicity in the figures we show only those functions which have appropriate dependence in the plane of the paper, which is taken to be the $`x`$-$`y`$ plane. At the upper left we show an $`xy`$-like function. It has two other t2g symmetry partners which are $`xz`$-like and $`yz`$-like. At the upper right we show one of the two Eg functions which is $`x^2y^2`$-like. These five t2g and Eg functions comprise the manifold of total angular momentum $`K=2`$ states. Within spherical symmetry all five of these states are degenerate in energy. In the lower left of Fig. 3 we show the $`z`$-like function of $`t_{1g}`$ symmetry. Its other two partners are obtained by cyclically permuting $`x`$, $`y`$, and $`z`$. These three functions comprise the manifold of total angular momentum $`K=1`$ states, which transform under rotation as a vector. Finally at the lower right we show the angular momentum $`K=0`$ state. Thus in spherical symmetry, the nine $`J=1`$ single phonon states give rise to three distinct energy manifolds which have degeneracies 1, 3, and 5, corresponding respectively to total angular momentum $`K=0`$, $`K=1`$, and $`K=2`$.

The simplest classical arguments do not reproduce the above results. For instance, one might argue that translation can occur equivalently along either of three equivalent coordinate axes. In each case, one can have the molecule oriented along the axis of translational motion or perpendicular to that axis. This argument would suggest that the nine levels break into a three-fold degenerate energy level in which the molecule is oriented longitudinally and a six-fold level in which the molecule is oriented transversely. This discussion shows that it is essential to treat the translation-rotation problem quantum mechanically to get the correct degeneracy.

## V NEUTRON SPECTRUM

In the experimental study of Fitzgerald et. al., neutron energy loss spectrum of H2 trapped in C60 was measured with an energy resolution of 0.3 meV. The spectrum shows surprisingly rich features. However the origin of these features were not successfully identified in detail. Since the observed neutron spectrum is a direct probe of the intermolecular potential between H2 molecules and C60 host lattice, it is very important to see if available atom-atom potentials can give a spectrum which is similar to the experimental data. A suitable analysis of the high resolution inelastic neutron scattering data in Ref. should, in principle, give a detailed information about the intermolecular potential between H2 molecules and the host lattice.

Figure 4 illustrates several possible transitions, involving both rotational and vibrational excitations, that could be observed in a neutron scattering experiment for H2 in solid C60. In order to estimate the intensities of these transitions and the corresponding neutron spectrum, in Appendix C we derive the inelastic neutron cross section for trapped H2 molecules in a powder sample at low temperature. Below we discuss the contribution to the total neutron spectrum from each of these transitions, labeled as $`T_A,\mathrm{},T_E`$, and then compare the calculated spectrum with experimental data using various atom-atom potentials.

We start with the transitions involving phonon creation in para hydrogen, as shown by $`T_D`$ in Fig.4. Because of the spin-dependent interaction between the proton and the neutron, processes in which a para molecule is not converted to an ortho molecule are forbidden, or more correctly speaking, are proportional to the coherent cross section $`b`$, which is very small compared to incoherent cross section $`b^{}`$. Hence, the transition $`T_D`$ will not have a noticeable contribution to the total cross section.

We next discuss the contribution to the total spectrum from processes in which either a $`(J=0)`$ molecule is converted to $`(J=1)`$ molecule (para-ortho conversion, labeled as $`T_A`$ in Fig. 4) or a single phonon is created (as shown by $`T_B`$). Our calculations presented so far indicate that both processes will give features around 14 meV in neutron spectrum.

In the Appendix C we find that the cross section due to para-ortho conversion, (indicated by the subscript $`01`$ is given by

$`{\displaystyle \frac{^2\sigma }{\mathrm{\Omega }E}})_{01}`$ $`=`$ $`{\displaystyle \frac{3}{/}}4N{\displaystyle \frac{k^{}}{k}}(1x)[b^{}j_1({\displaystyle \frac{1}{/}}2\kappa \rho )]^2e^{2W(\kappa )}{\displaystyle \underset{m}{}}\delta [E_L(E_c+E_m)],`$ (31)
where $`N`$ is the total number of H2 molecules, $`𝐤`$ ($`𝐤^{}`$) is wave vector of the incident (scattered) neutron, $`𝜿=𝐤^{}𝐤`$, $`x`$ is the fraction of H2 molecules which are ortho (odd $`J`$) molecules, $`\rho `$ is the separation between protons in the H2 molecule, $`b^{}`$ is the spin-dependent cross section in the proton-neutron pseudopotential, $`j_n`$ is the $`n`$th order spherical Bessel function, and $`W(\kappa )`$ is the Debye-Waller factor which we take to be $`\frac{1}{/}3\kappa ^2u^2`$. Also, $`E_L`$ is the energy loss of the neutron, and $`E_c+E_m`$ is the para-ortho conversion energy when the final state of the ortho has $`J_z=m`$.

Similarly, the cross section due to ortho-para conversion, $`\frac{^2\sigma }{\mathrm{\Omega }E})_{10}`$ has the same expression as Eq. (31) but now the factor $`(1x)`$ is replaced by $`x`$. Hence the ratio of the total cross section for ortho to para conversion to that of para to ortho conversion is $`(1x)`$ to $`x`$, where $`x`$ is the ortho concentration. Normally the ratio of energy gain to energy loss cross sections follows the Boltzmann factor. Here, the populations are set by $`x`$ rather than by the temperature.

We now discuss the cross section due to phonon creation on a $`(J=1)`$ molecule (indicated here by the subscript $`11`$), which is calculated in the Appendix C. These transitions are shown as $`T_B`$ in Fig. 4. The result requires a knowledge of the translation-rotation wave function of the H2 molecule. We find that

$`{\displaystyle \frac{^2\sigma }{\mathrm{\Omega }E}})_{11}`$ $`=`$ $`Nx{\displaystyle \frac{k^{}}{k}}b_{}^{}{}_{}{}^{2}{\displaystyle \underset{n=1}{\overset{4}{}}}S_{11,n}^{(1)},`$ (32)
where the cross section $`S_{11,n}^{(1)}`$ are given in Eqs. (C50), (C52), and (C63) of Appendix C.

In Fig. 5 TB represents the transitions from the $`(J=1,N=0)`$ levels to the manifold of nine energy levels of $`(J=1,N=1)`$. Accordingly, we expect several transitions with nonzero amplitude and thus rich features in the total neutron cross section.

Also one may consider the cross section integrated over energy, which is a usefull quantity to indicate the relative strength of the different transitions discussed above. The ratio, $`r_P`$, of the integrated neutron energy-loss cross section for phonon creation (process TB in Fig. 4) divided by that for para-ortho conversion (process TA in Fig. 4) was found in the Appendix C to be

$`r_P`$ $`=`$ $`{\displaystyle \frac{2}{/}}27\kappa ^2u^2{\displaystyle \frac{x[j_0(\frac{1}{/}2\kappa \rho )^2+2j_2(\frac{1}{/}2\kappa \rho )^2]}{(1x)j_1(\frac{1}{/}2\kappa \rho )^2}}.`$ (33)
This ratio is plotted as a function of $`\kappa `$ for $`x=3/4`$ in Fig. 6. Since this ratio is of order unity, the energy loss spectrum will display features due to both phonons and para-ortho conversion.

In appendix C we also calculate the zero phonon ortho cross section for the transition shown as $`T_E`$ in Fig. 4. Since the $`(J=1)`$ levels are in thermal equilibrium, in this case the ratio of the cross sections at energy gain to those of energy loss does satisfy detailed balance. The ratio of the total cross section (counting both energy loss and energy gain) for transitions within the $`(J=1)`$ ground manifold to that due to para to ortho conversion was found at zero temperature to be

$`r_{J=1}(T=0)`$ $`=`$ $`{\displaystyle \frac{x}{1x}}{\displaystyle \frac{4j_2(\frac{1}{/}2\kappa \rho )^2}{15j_1(\frac{1}{/}2\kappa \rho )^2}}.`$ (34)
Figure 6 shows that this ratio is quite small and therefore experimental observation of this transition (i.e. $`T_E`$) would be very difficult.

Figure 7 shows the neutron energy loss spectrum and the calculated total spectrum using the same potential, so called WS77 model, used by FitzGerald et. al. Even though the calculated spectum is wider than the experimental spectrum, it is still possible to make a one to one correspondence between calculation and experiment as is shown by arrows in Fig. 7. The top curve in this figure shows what the spectrum looks like if the orientational part of the potential is scaled by about half. The agreement between the data and calculations is somewhat better after this arbitrary scaling, indicating that the potential used is too anisotropic for the center of mass motion of H2 molecule but at the same time it is too weak for the orientational part of H2 (because it gives too small a result for $`\delta `$, the splitting of the $`(J=1)`$ ground manifold).

We also tested other potentials commonly used in the literature and these results are shown in Fig. 8. The top curve is from Novaco’s 6-12 potential which was developed to study hydrogen on graphite. Clearly this potential gives too low phonon energies and too little splitting of the $`(J=1)`$ levels for H2 in solid C60. The other two curves in Fig. 8 are 6-exp potentials tabulated in Ref.. The spectrum from these potentials does not agree with experiment either. We also searched the potential parameters $`A`$ and $`B`$ for 6-12 and $`A`$, $`B`$, and $`C`$ for 6-exp types of potentials. However we were not able to improve the fit to experiment using these atom-atom potentials. Hence, it seems that simple atom-atom potential does not describe the details of the H2-C60 interaction well. It is an open and important question to find a better potential can reproduce the experimental spectrum better. It is also of important to see how well the potentials obtained from density functional theory within local density approximation will do.

Finally, in addition to features observed near 14 meV, Fitzgerald et al. also observed a feature at about 28 meV in the energy gain time-of-flight spectrum. This energy is about twice that of either the para-ortho conversion energy or the energy of the translational phonon for an H2 molecule in an octahedral interstitial site. Clearly this feature represents the energy of two excitations, but it was not clear whether these would be two phonons, one phonon and one ortho-para transition or two ortho-para transitions. In Fig. 9 we show the temperature dependence of the total intensity of this feature. This temperature dependence follows a thermal activation with an energy of about 14 meV. Thus the initial state must consist of one thermally excited phonon and the transition observed destroys one thermal phonon and converts one ortho molecule (which occurs with temperature-independent probability $`x`$) to a para molecule, thus giving the observed energy of about 28 meV.

## VI Conclusions

Our results indicate that the coupled phonon-roton problem is a rich one. For the light molecules of H2 where the splitting of rotational levels is large compared to most lattice vibrational modes, one is in a so-called weak-coupling limit where the interactions between rotons and translational phonons can be treated perturbatively. Even at this level one recovers an interesting structure.

Needless to say, we hope that the calculations in this paper will motivate more detailed experiments at higher resolution to elucidate the structure of the roton-phonon spectrum.

We may summarize our main conclusions as follows:

$``$ We have presented a systematic perturbative approach to the calculation of the roton-phonon spectrum of hydrogen molecules in confined geometry. Our calculations agree with the group theoretical analysis for the geometries considered here.

$``$ In a general way, the techniques of this paper (use of the atom-atom potential combined with perturbation theory) may prove useful to treat hydrogen molecules in other confined geometries, in particular in or on nanotubes. We are currently analyzing this situation.

$``$ We give the first calculation of the expected energy loss spectrum from hydrogen in C60 in the energy range where phonons and para-ortho conversion both are important. We find that none of the traditional 6-12 and 6-exp types of potentials give good results for the detailed energy dependence of the observed phonon spectrum, although the WS77 potential we used was definitely the most satisfactory. It is a theoretical challenge to determine a potential which fully reproduces the observed spectrum.

$``$ We identify the feature at 28 meV in the energy gain spectrum as consisting of conversion of one ortho molecule to a para molecule combined with annihilation of a single phonon. This identification is uniquely indicated by the temperature dependence of this feature.

## VII acknowledgement

We acknowledge partial support from the Israel-US Binational Science Foundation.

## A Atom-Atom Potential and $`A_l^m`$

We model the interactions between the hydrogen molecule and the surrounding cage of C60 molecules using an atom-atom potential. Unless otherwise indicated, all the results reported in this paper are obtained from the same potential $`A/r^6+B\mathrm{exp}(Cr)`$ that is used in Ref. (where $`A=5.94`$ eV Å6, $`B=678.2`$ eV, and $`C=3.67`$ Å-1).

We consider two cases depending on the orientational state of C60 molecules. When the molecules in the surrounding cage are orientationally disordered, we distribute the carbon centers uniformly over the surface of a sphere. This case corresponds to the octahedral symmetry discussed in the text. The resulting integration of the atom-atom potential over a spherical surface is done analytically in Ref. and therefore is not given here. For the Pa$`\overline{3}`$ symmetry, the C60 molecules are rotated according to their Pa$`\overline{3}`$ settings and then the total potential and $`A_l^m`$’s are calculated on a mesh points of a cube centered at the octahedral site. Below we derive a convenient way to obtain the $`A_l^m`$’s from the atom-atom potential.

We write the potential, $`V_{\mathrm{H}\mathrm{C}}`$ between a single H atom and a single C atom as

$`V_{\mathrm{H}\mathrm{C}}`$ $`=`$ $`F(r),`$ (A1)
where $`𝐫`$ is the displacement of the C atom relative to to the H atom. Thus the interaction, $`V`$(H2) of a H2 molecule with a C atom can be written as

$`V(\mathrm{H}_2)`$ $`=`$ $`{\displaystyle \underset{\sigma =\pm 1}{}}F([r^2+{\displaystyle \frac{1}{/}}4\rho ^2+\sigma \rho 𝐫\widehat{n}]^{1/2}),`$ (A2)
where now $`𝐫`$ is the displacement of the C atom relative to the center of the H2 molecule whose atoms are at positions $`\pm \frac{1}{/}2\rho \widehat{n}`$, where $`\widehat{n}`$ is a unit vector specifying the orientation of the molecular axis of the H2 molecule. Then

$`A_{2l}^m`$ $`=`$ $`{\displaystyle \underset{\sigma }{}}{\displaystyle \underset{i}{}}{\displaystyle Y_{2l}^m(\widehat{n})^{}F([r_i^2+\frac{1}{/}4\rho ^2+\sigma \rho 𝐫_i\widehat{n}]^{1/2})𝑑\mathrm{\Omega }},`$ (A3)
where $`d\mathrm{\Omega }`$ indicates an integration over all orientations of $`\widehat{n}`$ and the sum over $`i`$ is over all neighboring carbon atoms. We use this to get

$`A_0^0`$ $``$ $`V_0=2\sqrt{\pi }{\displaystyle \underset{i}{}}{\displaystyle _1^1}F([r_i^2+{\displaystyle \frac{1}{/}}4\rho ^2+\rho r_ix]^{1/2})𝑑x.`$ (A4)
To get the $`A_l^m`$’s for $`l>0`$ we write

$`{\displaystyle \underset{\sigma }{}}F([r_i^2+{\displaystyle \frac{1}{/}}4\rho ^2+\sigma \rho 𝐫_i\widehat{n}]^{1/2})`$ $`=`$ $`{\displaystyle \underset{L}{}}B_{2L}(r_i)Y_{2L}^0(\theta _{r,n}),`$ (A5)
where $`\theta _{r,n}`$ is the angle between the vectors $`𝐫_i`$ and $`\widehat{n}`$. We have that

$`B_{2L}(r_i)`$ $`=`$ $`2\pi {\displaystyle \underset{\sigma }{}}{\displaystyle _0^\pi }F([r_i^2+{\displaystyle \frac{1}{/}}4\rho ^2+\sigma \rho 𝐫_i\mathrm{cos}\theta ]^{1/2})Y_{2L}^0(\theta )\mathrm{sin}\theta d\theta .`$ (A6)
Now substitute Eq. (A5) into Eq. (A3) to get

$`A_{2l}^m`$ $`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle Y_{2l}^m(\widehat{n})^{}\underset{L}{}B_{2L}(r_i)Y_{2L}^0(\theta _{r,n})d\mathrm{\Omega }}.`$ (A7)
Using the addition theorem for spherical harmonics we have

$`A_{2l}^m`$ $`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle Y_{2l}^m(\widehat{n})^{}\underset{L}{}B_{2L}(r_i)\sqrt{4\pi /(2L+1)}\underset{\nu }{}Y_{2L}^\nu (\widehat{n})Y_{2L}^\nu (\widehat{𝐫}_i)^{}d\mathrm{\Omega }}`$ (A8)
$`=`$ $`{\displaystyle \underset{i}{}}B_{2l}(r_i)\sqrt{4\pi /(2l+1)}Y_{2l}^m(\widehat{𝐫}_i)^{}.`$ (A9)
For $`A_2^m`$ we get

$`A_2^m`$ $`=`$ $`2\pi {\displaystyle \underset{i}{}}Y_2^m(\widehat{𝐫}_i)^{}{\displaystyle _1^1}(3x^21)F([r_i^2+{\displaystyle \frac{1}{/}}4\rho ^2+r_i\rho x]^{1/2})𝑑x.`$ (A10)
For power-law functions $`F`$ (i.e. $`F1/r^{2n}`$), this integral can be done analytically.

## B Spherical Cavity

In this appendix we apply our formalism discussed in the text to a simple toy model to utilize the main physics of quantum roton-phonon dynamics of a H2 molecule confined in a spherically symmetric cavity for which the potential differs perturbatively from harmonic.

### 1 Orientationally Dependent Potential

For a diatomic molecule for which the spherical part of the potential is that of an isotropic spherical oscillator, we take the orientationally dependent part of the potential to be

$`U(𝐫,\mathrm{\Omega })`$ $`=`$ $`f(r)\left[(\widehat{x}\mathrm{sin}\theta \mathrm{cos}\varphi +\widehat{y}\mathrm{sin}\theta \mathrm{sin}\varphi +\widehat{z}\mathrm{cos}\theta )^2{\displaystyle \frac{1}{/}}3\right],`$ (B1)
where $`\widehat{x}x/r`$, $`\widehat{y}y/r`$, and $`\widehat{z}=z/r`$.

This potential can be written in the canonical form of Eq. (2) with

$`A_2^m`$ $`=`$ $`{\displaystyle \frac{8\pi }{15}}f(r)Y_2^m(\widehat{r})^{}.`$ (B2)
### 2 Energy Shift of the $`J=1`$ Manifold

To evaluate Eq. (20) for the shift in the center of gravity of the $`J=1`$ zero phonon levels, we need the wave function of the ground state, namely

$`\psi _0(𝐫)`$ $`=`$ $`\alpha e^{r^2/(4\sigma ^2)}.`$ (B3)
where $`\alpha =\sigma ^{3/2}(2\pi )^{3/4}`$. Also we can write the two phonon excited states (for spherical symmetry) as

$`\psi _{2,m}^{(L=2)}`$ $`=`$ $`\beta (r/\sigma )^2Y_2^m(\widehat{𝐫})e^{r^2/(4\sigma ^2)},`$ (B4)
for $`m=2,1,0,1,2`$ and for angular momentum $`L=2`$ and where $`\beta =\sigma ^{3/2}\sqrt{2/15}(2\pi )^{1/4}`$. The sixth two-phonon state is an $`s`$-wave state, whose wave function we do not need. We will also need the $`L=2`$ (d-wave) four phonon states which are

$`\psi _{4,m}^{(L=2)}`$ $`=`$ $`\gamma [(r/\sigma )^47(r/\sigma )^2]Y_2^m(\widehat{𝐫})e^{r^2/(4\sigma ^2)},`$ (B5)
for $`m=2,1,0,1,2`$ and for angular momentum $`L=2`$ and where $`\gamma =\sigma ^{3/2}\sqrt{1/105}(2\pi )^{1/4}`$.

Now we assume the following polynomial fit for $`f(r)`$:

$`f(r)=\gamma _2(r/\sigma )^2+\gamma _4(r/\sigma )^4+\gamma _6(r/\sigma )^6.`$ (B6)
We then find

$`|0|A_2^m(𝐫)|\psi _{2,m}^{(L=2)}|`$ $`=`$ $`4\sqrt{{\displaystyle \frac{\pi }{15}}}|\gamma _2+7\gamma _4+63\gamma _6|4\sqrt{{\displaystyle \frac{\pi }{15}}}\mathrm{\Gamma }`$ (B7)
and

$`|0|A_2^m(𝐫)|\psi _{4,m}^{(L=2)}|`$ $`=`$ $`4\sqrt{{\displaystyle \frac{14\pi }{15}}}|\gamma _4+18\gamma _6|`$ (B8)
Thus we have

$`\mathrm{\Delta }E`$ $`=`$ $`{\displaystyle \frac{4}{15}}{\displaystyle \frac{(\gamma _2+7\gamma _4+63\gamma _6)^2}{\mathrm{}\omega }}{\displaystyle \frac{28}{15}}{\displaystyle \frac{(\gamma _4+18\gamma _6)^2}{\mathrm{}\omega }}.`$ (B9)
From numerics we get

$`A_2^0(z)=0.07226r^4+0.0348r^6.`$ (B10)
For convenience we take $`\sigma =0.25\AA `$. Then $`A_2^0`$ is of the form of Eq. (B6) with

$`\gamma _4=0.07226\sigma ^4,\gamma _6=0.0348\sigma ^6.`$ (B11)
$`\gamma _4`$ $`=`$ $`0.07226/256=0.282\mathrm{meV}`$ (B12)
$`\gamma _6`$ $`=`$ $`0.0348/4096=0.0084\mathrm{meV}.`$ (B13)
we evaluate the first and second terms on the right-hand side of Eq. (B9) to be 0.115 meV and 0.025 meV, respectively. Thus we have

$`\mathrm{\Delta }E`$ $`=`$ $`0.14\mathrm{meV}.`$ (B14)
Notice that $`\mathrm{\Delta }E`$ is a very strong function of $`\sigma `$. For instance, if you take $`\sigma =0.26\AA `$, you get $`\gamma _4=0.33`$ meV and $`\gamma _6=0.011`$ meV in which case $`\mathrm{\Delta }E=0.19`$ meV.

### 3 Effect of Translation-Rotation Coupling on the $`J=1`$ One Phonon Manifold

In the absence of coupling between translations and rotations we characterize the single-phonon states by phonon angular momentum $`L_P`$, so that

$`|L_P=\pm 1`$ $`=`$ $`\left({\displaystyle \frac{x\pm iy}{\sigma }}\right)\psi _0(𝐫),|L_P=0=(z/\sigma )\psi _0(𝐫).`$ (B15)
We now wish to include the effect of the perturbation of the form of Eq. (2) when the coefficients are as in Eq. (B2), with $`f(r)`$ given by Eq. (B6). We know that states are now characterized by the total angular momentum $`𝐊=𝐋_𝐏+𝐉`$. So the energy of the $`K=2`$ manifold is given by

$`E(K=2)`$ $`=`$ $`L_P=1,J_z=1|U(𝐫,\mathrm{\Omega })|L_P=1,J_z=1`$ (B16)
$`=`$ $`{\displaystyle \frac{1}{15}}{\displaystyle \frac{𝑑𝐫\left|\frac{xiy}{\sigma }\right|^2e^{r^2/(2\sigma ^2)}f(r)\frac{3z^2r^2}{r^2}}{𝑑𝐫\left|\frac{xiy}{\sigma }\right|^2e^{r^2/(2\sigma ^2)}}}J_z=1|(3J_z^22)|J_z=1`$ (B17)
$`=`$ $`{\displaystyle \frac{2𝑑𝐫r^2f(r)e^{r^2/(2\sigma ^2)}}{225\sigma ^2𝑑𝐫e^{r^2/(2\sigma ^2)}}}={\displaystyle \frac{2}{/}}15\mathrm{\Gamma },`$ (B18)
where $`f(r)`$ and $`\mathrm{\Gamma }`$ are defined in Eq. (B6) and Eq. (B7), respectively.

Similarly, one can evaluate the Hamiltonian in the manifold of states $`\varphi _1=|L_P=1,J_z=0`$ and $`\varphi _2=|L_P=0,J_z=1`$. The Hamiltonian matrix in this basis is found to be

$``$ $`=`$ $`\mathrm{\Gamma }\left[\begin{array}{cc}\frac{4}{/}15& \frac{2}{/}5\\ \frac{2}{/}5& \frac{4}{/}15\end{array}\right].`$ (B21)
This matrix has an eigenvalue $`\frac{2}{/}15\mathrm{\Gamma }`$ which is associated with the $`K=2`$, $`K_z=1`$ state and the new eigenvalue for the $`K=1`$ manifold, $`E(K=1)=\frac{2}{/}3\mathrm{\Gamma }`$.

Similarly, one can evaluate the Hamiltonian in the manifold of states $`\varphi _1=|L_P=1,J_z=1`$, $`\varphi _2=|L_P=0,J_z=0`$ and $`\varphi _3=|L_P=1,J_z=1`$. The Hamiltonian matrix in this basis is found to be

$``$ $`=`$ $`\mathrm{\Gamma }\left[\begin{array}{ccc}\frac{2}{/}15& \frac{2}{/}5& \frac{4}{/}5\\ \frac{2}{/}5& \frac{8}{/}15& \frac{2}{/}5\\ \frac{4}{/}5& \frac{2}{/}5& \frac{2}{/}15\end{array}\right].`$ (B25)
In this manifold we reproduce the eigenvalues for $`K=2`$ and $`K=1`$. The new eigenvalue is $`E(K=0)=\frac{4}{/}3\mathrm{\Gamma }`$.

## C Neutron Scattering Cross Section

### 1 GENERAL FORMULATION

Following Elliott and Hartmann, we write

$`V(𝐫𝐫_n)`$ $`=`$ $`{\displaystyle \frac{2\pi \mathrm{}}{m_0}}\delta (𝐫𝐫_n)\left[b+b^{}(𝝈𝐈)\right],`$ (C1)
where $`m_0`$ is the neutron mass, $`𝝈`$ is the neutron spin, $`𝐫`$ is the coordinate of the proton, $`𝐫_n`$ the coordinate of the neutron, $`I`$ is the proton spin, and $`b`$ and $`b^{}`$ are the coherent and incoherent scattering lengths for this scattering. Since $`b`$ is very small, we drop that term from now on. The differential scattering cross section is

$`{\displaystyle \frac{^2\sigma }{\mathrm{\Omega }E}}`$ $`=`$ $`{\displaystyle \frac{k^{}}{k}}{\displaystyle \underset{if}{}}P_i\delta (EE_i+E_f)|V|^2,`$ (C2)
where $`E=\mathrm{}^2[(k^{})^2k^2]/(2m_0)`$ and the sum is over all states of the system. Here the potential is

$`V=b^{}{\displaystyle \underset{j\alpha }{}}e^{i𝜿𝐑_{j,\alpha }}𝝈I_{j,\alpha },`$ (C3)
where $`𝜿=𝐤^{}𝐤`$, $`j`$ labels molecules and $`\alpha =1,2`$ the atoms within a molecule. Performing the sum over $`\alpha `$ we get

$`V=b^{}{\displaystyle \underset{j}{}}e^{i𝜿𝐑_j}\left((𝝈I_j)\mathrm{cos}({\displaystyle \frac{1}{/}}2𝜿𝝆)+i\mathrm{sin}({\displaystyle \frac{1}{/}}2𝜿𝝆)[𝝈(𝐈_{j1}𝐈_{j2})]\right),`$ (C4)
where $`𝐈_j=𝐈_{j1}+𝐈_{j2}`$. The first term acts only on ortho molecules because for paras the total spin is zero and the second term causes transitions between ortho and para molecules. So we write the scattering cross section as the sum of three terms, the first of which represents scattering from an ortho molecule and others ortho-para conversion or the reverse. Thus

$`{\displaystyle \frac{^2\sigma }{\mathrm{\Omega }E}}`$ $`=`$ $`{\displaystyle \frac{k^{}}{k}}\left[Nx𝒮_{11}+Nx𝒮_{10}+N(1x)𝒮_{01}\right],`$ (C5)
where $`N`$ is the total number of molecules and $`x`$ is the ortho concentration. Because there are no correlations between nuclear spins each cross section is actually a sum over cross sections for each molecule:

$`𝒮_\beta `$ $`=`$ $`{\displaystyle \underset{j}{}}𝒮_{\beta j},`$ (C6)
where $`j`$ labels the molecule, $`\beta `$ is $`01`$, etc., and

$`𝒮_{01,j}`$ $`=`$ $`{\displaystyle \underset{J_i=0,J_f=1}{}}P_i\delta (EE_i+E_f)\left|f|b^{}e^{i𝜿𝐑_j}\mathrm{sin}({\displaystyle \frac{1}{/}}2𝜿𝝆)[𝝈(𝐈_{j1}𝐈_{j2})]|i_T\right|^2`$ (C7)
$`𝒮_{10,j}`$ $`=`$ $`{\displaystyle \underset{J_i=1,J_f=0}{}}P_i\delta (EE_i+E_f)\left|f|b^{}e^{i𝜿𝐑_j}\mathrm{sin}({\displaystyle \frac{1}{/}}2𝜿𝝆)[𝝈(𝐈_{j1}𝐈_{j2})]|i_T\right|^2`$ (C8)
$`𝒮_{11,j}`$ $`=`$ $`{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f)\left|f|b^{}e^{i𝜿𝐑_j}\mathrm{cos}({\displaystyle \frac{1}{/}}2𝜿𝝆)[𝝈𝐈]|i_T\right|^2,`$ (C9)
where the sums are over states for the fixed species (ortho or para) of molecule as indicated and the subscript T indicates that the wavefunctions include nuclear spin functions.

Now we perform the sum over the spin states of the neutron and proton to obtain the results

$`𝒮_{01,j}`$ $`=`$ $`{\displaystyle \frac{3}{/}}4(b^{})^2{\displaystyle \underset{J_i=0,J_f=1}{}}P_i\delta (EE_i+E_f)\left|f|e^{i𝜿𝐑_j}\mathrm{sin}({\displaystyle \frac{1}{/}}2𝜿𝝆)|i\right|^2`$ (C10)
$`𝒮_{10,j}`$ $`=`$ $`{\displaystyle \frac{1}{/}}4(b^{})^2{\displaystyle \underset{J_i=1,J_f=0}{}}P_i\delta (EE_i+E_f)\left|f|e^{i𝜿𝐑_j}\mathrm{sin}({\displaystyle \frac{1}{/}}2𝜿𝝆)|i\right|^2`$ (C11)
$`𝒮_{11,j}`$ $`=`$ $`{\displaystyle \frac{1}{/}}2(b^{})^2{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f)\left|f|e^{i𝜿𝐑_j}\mathrm{cos}({\displaystyle \frac{1}{/}}2𝜿𝝆)|i\right|^2,`$ (C12)
where now states $`|f`$ and $`|i`$ no longer include nuclear spin wavefunctions. We write

$`e^{i𝜿𝐑_j}`$ $`=`$ $`e^{i𝜿(𝐑_j^{(0)}+𝐮_j)}e^{i𝜿𝐑_j^{(0)}}e^{\frac{1}{/}2(𝜿u_j)^2}\left[1+i(𝜿𝐮_j)\right]`$ (C13)
$``$ $`e^We^{i𝜿𝐑_j^{(0)}}\left[1+i(𝜿𝐮_j)\right],`$ (C14)
where $`𝐑_j^{(0)}`$ is the equilibrium value of $`𝐑_j`$ and $`W\frac{1}{/}6\kappa ^2u^2\frac{1}{/}6\kappa ^2u_x^2+u_y^2+u_z^2`$. Since spherical harmonics of degree higher than two do not affect the manifolds of $`J=0`$ or $`J=1`$, we now use

$`\mathrm{cos}({\displaystyle \frac{1}{/}}2𝜿𝝆)`$ $`=`$ $`j_0({\displaystyle \frac{1}{/}}2\kappa \rho )4\pi j_2({\displaystyle \frac{1}{/}}2\kappa \rho ){\displaystyle \underset{\nu }{}}Y_2^n(\widehat{𝜿})^{}Y_2^n(\widehat{𝝆})`$ (C15)
and

$`\mathrm{sin}({\displaystyle \frac{1}{/}}2𝜿𝝆)=4\pi j_1({\displaystyle \frac{1}{/}}2\kappa \rho ){\displaystyle \underset{\nu }{}}Y_1^n(\widehat{𝜿})^{}Y_1^n(\widehat{𝝆}).`$ (C16)
We expand in displacements to get

$`𝒮_{01,j}`$ $`=`$ $`(4\pi )^2A{\displaystyle \underset{J_i=0,J_f=1}{}}P_i\delta (EE_i+E_f)f|\left[1+i𝜿𝐮_j\right]{\displaystyle \underset{\nu }{}}Y_1^\nu (\widehat{𝜿})^{}Y_1^\nu (\widehat{𝝆})|i`$ (C18)
$`\times i|\left[1i𝜿𝐮_j\right]{\displaystyle \underset{\mu }{}}Y_1^\mu (\widehat{𝜿})Y_1^\mu (\widehat{𝝆})^{}|f,`$
$`𝒮_{10,j}`$ $`=`$ $`(4\pi )^2B{\displaystyle \underset{J_i=1,J_f=0}{}}P_i\delta (EE_i+E_f)f|\left[1+i𝜿𝐮_j\right]`$ (C20)
$`{\displaystyle \underset{\nu }{}}Y_1^\nu (\widehat{𝜿})^{}Y_1^\nu (\widehat{𝝆})|ii|\left[1i𝜿𝐮_j\right]{\displaystyle \underset{\mu }{}}Y_1^\mu (\widehat{𝜿})Y_1^\mu (\widehat{𝝆})^{}|f,`$
where $`A=\frac{3}{/}4e^{2W}[b^{}j_1(\frac{1}{/}2\kappa \rho )]^2`$ and $`B=\frac{1}{/}4e^{2W}[b^{}j_1(\frac{1}{/}2\kappa \rho )]^2`$ and

$`𝒮_{11,j}`$ $`=`$ $`{\displaystyle \frac{1}{/}}2(b^{})^2{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f)`$ (C23)
$`\times f|\left[1+i𝜿𝐮_j\right]\left[j_0({\displaystyle \frac{1}{/}}2\kappa \rho )+4\pi j_2({\displaystyle \frac{1}{/}}2\kappa \rho ){\displaystyle \underset{\nu }{}}Y_2^\nu (\widehat{𝜿})^{}Y_2^\nu (\widehat{𝝆})\right]|i`$
$`\times i|\left[1i𝜿𝐮_j\right]\left[j_0({\displaystyle \frac{1}{/}}2\kappa \rho )+4\pi j_2({\displaystyle \frac{1}{/}}2\kappa \rho ){\displaystyle \underset{\mu }{}}Y_2^\mu (\widehat{𝜿})Y_2^\mu (\widehat{𝝆})^{}\right]|f,`$
Since the phonon energy is much larger than the orientational energy, we may classify contributions according the number of phonons that are involved. In the notation of Eq. (C6) we write

$`𝒮_\beta =𝒮_\beta ^{(0)}+𝒮_\beta ^{(1)},`$ (C24)
where $`𝒮_\beta ^{(0)}`$ corresponds to a zero-phonon process and $`𝒮_\beta ^{(1)}`$ to a process in which one phonon is created or destroyed. Thus

$`𝒮_{01}^{(0)}`$ $`=`$ $`(4\pi )^2A{\displaystyle \underset{J_i=0,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu \nu }{}}f|Y_1^\nu (\widehat{𝝆})|ii|Y_1^\mu (\widehat{𝝆})^{}|fY_1^\nu (\widehat{𝜿})^{}Y_1^\mu (\widehat{𝜿})`$ (C25)
$`𝒮_{01}^{(1)}`$ $`=`$ $`(4\pi )^2A{\displaystyle \underset{J_i=0,J_f=1}{}}P_i\delta (EE_i+E_f)`$ (C27)
$`\times {\displaystyle \underset{\mu \nu \alpha \beta }{}}f|u_\alpha ^{}Y_1^\nu (\widehat{𝝆})|ii|u_\beta ^{}Y_1^\mu (\widehat{𝝆})^{}|f\kappa _\alpha \kappa _\beta Y_1^\nu (\widehat{𝜿})^{}Y_1^\mu (\widehat{𝜿}).`$
Here and below we use spherical components of a vector $`𝐯`$: $`v_{\pm 1}=(v_x\pm iv_y)/\sqrt{2}`$ and $`v_0=v_z`$. Similarly

$`𝒮_{10}^{(0)}=(4\pi )^2B{\displaystyle \underset{J_i=1,J_f=0}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu \nu }{}}f|Y_1^\nu (\widehat{𝝆})|ii|Y_1^\mu (\widehat{𝝆})^{}|fY_1^\nu (\widehat{𝜿})^{}Y_1^\mu (\widehat{𝜿}),`$ (C28)
$`𝒮_{10}^{(1)}`$ $`=`$ $`(4\pi )^2B{\displaystyle \underset{J_i=1,J_f=0}{}}P_i\delta (EE_i+E_f)`$ (C30)
$`\times {\displaystyle \underset{\mu \nu }{}}f|u_\alpha ^{}Y_1^\nu (\widehat{𝝆})|ii|u_\beta ^{}Y_1^\mu (\widehat{𝝆})^{}|f\kappa _\alpha \kappa _\beta Y_1^\nu (\widehat{𝜿})^{}Y_1^\mu (\widehat{𝜿}),`$
$`S_{11}^{(0)}`$ $`=`$ $`(4\pi )^2C{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu ,\nu }{}}f|Y_2^\mu (\widehat{𝝆})|ii|Y_2^\nu (\widehat{𝝆})|fY_2^\mu (\widehat{𝜿})^{}Y_2^\nu (\widehat{𝜿})^{},`$ (C31)
where $`C=\frac{1}{/}2e^{2W}[b^{}j_2(\frac{1}{/}2\kappa \rho )]^2`$ and

$`𝒮_{11}^{(1)}=D_0{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\alpha \beta }{}}f|u_\alpha ^{}|ii|u_\beta |f\kappa _\alpha ^{}\kappa _\beta `$ (C35)
$`+4\pi D_1{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu \alpha \beta }{}}f|u_\alpha ^{}Y_2^\mu (\widehat{𝝆})|ii|u_\beta ^{}|f\kappa _\alpha \kappa _\beta Y_2^\mu (\widehat{𝜿})^{}`$
$`+4\pi D_1{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu \alpha \beta }{}}f|u_\alpha ^{}|ii|u_\beta ^{}Y_2^\mu (\widehat{𝝆})|f\kappa _\alpha \kappa _\beta Y_2^\mu (\widehat{𝜿})^{}`$
$`+(4\pi )^2D_2{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu \nu \alpha \beta }{}}f|u_\alpha ^{}Y_2^\nu (\widehat{𝝆})^{}|ii|u_\beta ^{}Y_2^\mu (\widehat{𝝆})|f\kappa _\alpha \kappa _\beta Y_2^\mu (\widehat{𝜿})^{}Y_2^\nu (\widehat{𝜿})`$
$`=`$ $`{\displaystyle \underset{n=1}{\overset{4}{}}}S_{11;n}^{(1)},`$ (C36)
where $`D_n=\frac{1}{/}2(b^{})^2e^{2W}j_0(\frac{1}{/}2\kappa \rho )^{2n}j_2(\frac{1}{/}2\kappa \rho )^n`$ and $`S_{11;n}^{(1)}`$ is the contribution to the one-phonon ortho cross section from the $`n`$th term in the first equality.

Note the existence of terms in which a phonon and a roton are created, the system evolves and finally a phonon is destroyed. This type of process can only occur when the system supports roton-phonon interactions. All the terms $`𝒮_{11;n}^{(1)}`$ correspond approximately to the phonon energy.

### 2 POWDER AVERAGE AT LOW TEMPERATURE

Here we restrict attention to the energy loss spectrum at low temperature when there are no thermal phonons present. Also, we now take the powder average. This corresponds to actual experimental situation in Ref. , but would also be a reasonable approximation to take account of the differently oriented symmetry axes of the various octahedral interstitial sites. Below we calculate the cross sections for the following processes; (a) energy loss by conversion, (b) energy gain by conversion, (c) single phonon energy loss, and finally (d) zero phonon transition from $`(J=1,M=0)`$ to $`(J=1,M=\pm 1)`$.

#### a Energy Loss by Conversion

We have

$`𝒮_{01}^{(0)}`$ $`=`$ $`(4\pi )A{\displaystyle \underset{J_i=0,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu }{}}f|Y_1^\mu (\widehat{𝝆})|ii|Y_1^\mu (\widehat{𝝆})^{}|f,`$ (C37)
where $``$ indicates a powder average. The initial state is the $`J=0,J_z=0`$ zero-phonon state, which we write as

$`\psi _i`$ $`=`$ $`{\displaystyle \underset{𝐫}{}}c_i(𝐫)|𝐫;J=0;J_z=0,`$ (C38)
where $`c_i(𝐫)`$ is the amplitude of the wave function at the mesh point $`𝐫`$. The final state is a $`J=1`$ zero-phonon state, which we similarly write as

$`\psi _{f,m}`$ $`=`$ $`{\displaystyle \underset{𝐫,M}{}}c_{f,m}(𝐫,M)|𝐫;J=1;J_z=M`$ (C39)
and whose energy relative to the $`J=0`$ state is

$`E_{f,m}=E_c+E_m.`$ (C40)
If $`E_L=E`$ is the energy loss, we may write

$`𝒮_{01}^{(0)}(E_L)`$ $`=`$ $`A{\displaystyle \underset{m}{}}\delta [E_L(E_c+E_m)]{\displaystyle \underset{\mu }{}}\left|{\displaystyle \underset{𝐫}{}}c_{f,m}(𝐫,\mu )^{}c_i(𝐫)\right|^2.`$ (C41)
To a good approximation the zero-phonon wave functions for $`J=1`$ can be chosen to be composed of a single value of $`J_z`$. Thus we may label the wave functions so that $`\mu =m`$:

$`𝒮_{01}^{(0)}(E_L)`$ $`=`$ $`A{\displaystyle \underset{m}{}}\delta [E_L(E_c+E_m)]\left|{\displaystyle \underset{𝐫}{}}c_{f,m}(𝐫,m)^{}c_i(𝐫)\right|^2.`$ (C42)
The corresponding integrated intensity is

$`I^{(0)}`$ $``$ $`{\displaystyle 𝑑E_L𝒮_{01}^{(0)}}=A{\displaystyle \underset{m}{}}\left|{\displaystyle \underset{𝐫}{}}c_{f,m}(𝐫,m)^{}c_i(𝐫)\right|^2.`$ (C43)
The inner product of the $`J=0`$ wave function and the spatial part of the $`J=1`$ zero-phonon states is essentially unity. So

$`I^{(0)}`$ $`=`$ $`3A.`$ (C44)
#### b Energy Gain by Conversion

Here we give a similar analysis of the energy-gain spectrum at low temperature due to ortho-para conversion. The derivation is similar to that for para-ortho conversion so we only quote the results:

$`𝒮_{10}^{(0)}(E_L)`$ $`=`$ $`B{\displaystyle \underset{m}{}}P_m\delta [E(E_cE_m)]\left|{\displaystyle \underset{𝐫}{}}c_{i,m}(𝐫,m)^{}c_f(𝐫)\right|^2,`$ (C45)
where $`P_m`$ is the probability that the $`J=1,J_z=m`$ state is occupied and the role of initial and final states is interchanged from the para to ortho processes. The corresponding integrated intensity is

$`I^{(0)}`$ $``$ $`{\displaystyle 𝑑E𝒮_{10}^{(0)}}=B{\displaystyle \underset{m}{}}P_m\left|{\displaystyle \underset{𝐫}{}}c_{i,m}(𝐫,m)^{}c_f(𝐫)\right|^2`$ (C46)
$`=`$ $`B.`$ (C47)
Since $`B=3A`$ we see that ratio of the total cross section for ortho to para conversion to that of para to ortho conversion is $`(1x)`$ to $`x`$, where $`x`$ is the ortho concentration. Normally the ratio of energy gain to energy loss cross sections follows the Boltzmann factor. Here, the populations are set by $`x`$ rather than by the temperature.

#### c Single Phonon Energy Loss

We have the powder average of $`S_{11;1}^{(1)}`$ of Eq. (C36) as

$`S_{11;1}^{(1)}`$ $`=`$ $`{\displaystyle \frac{1}{/}}3\kappa ^2D_0{\displaystyle \underset{J_i=1,J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{L}{}}|f|u_L|i|^2`$ (C48)
and the corresponding integrated intensity is

$`I_1^{(1)}`$ $``$ $`{\displaystyle 𝑑E_LS_{11;1}^{(1)}(E_L)}={\displaystyle \frac{1}{/}}3\kappa ^2u^2D_0.`$ (C49)
In terms of the amplitudes of the wave function on the mesh points, the above result is

$`S_{11;1}^{(1)}`$ $`=`$ $`{\displaystyle \frac{1}{/}}3\kappa ^2D_0{\displaystyle \underset{i,f}{}}P_i\delta (E_LE_f+E_i){\displaystyle \underset{L}{}}\left|{\displaystyle \underset{M,𝐫}{}}c_i(M,𝐫)c_f(M,𝐫)r_L\right|^2.`$ (C50)
Also we obtain the powder average of $`S_{11;2}^{(1)}`$ and $`S_{11;3}^{(1)}`$ of Eq. (C36) as

$`S_{11;2}^{(1)}(E_L)`$ $`=`$ $`S_{11;3}^{(1)}(E_L)^{}={\displaystyle \frac{2}{5}}\sqrt{{\displaystyle \frac{8\pi }{15}}}D_1\kappa ^2{\displaystyle \underset{i,f}{}}P_i\delta (E_LE_f+E_i)`$ (C52)
$`\times {\displaystyle \underset{M,M^{}}{}}C(112;M,M^{})(1)^{M+M^{}}f|u_MT_2^{M+M^{}}(𝐉)|ii|u_M^{}|f,`$
where the $`T_2^M(𝐉)`$ are the operator equivalents of the spherical harmonics:

$`T_2^{\pm 2}(𝐉)`$ $`=`$ $`\sqrt{{\displaystyle \frac{15}{32\pi }}}J_\pm ^2,T_2^{\pm 1}(𝐉)=\sqrt{{\displaystyle \frac{15}{32\pi }}}(J_zJ_\pm +J_\pm J_z),T_2^0(𝐉)=\sqrt{{\displaystyle \frac{5}{16\pi }}}(3J_z^22).`$ (C53)
Here

$`i|u_M^{}|f`$ $`=`$ $`{\displaystyle \underset{\mu ,𝐫}{}}c_i(\mu ,𝐫)^{}c_f(\mu ,𝐫)r_M^{}.`$ (C54)
and

$`f|u_MT_2^{M+M^{}}(𝐉)|i`$ $`=`$ $`{\displaystyle \frac{5}{\sqrt{8\pi }}}{\displaystyle \underset{\mu ,𝐫}{}}c_i(\mu ,𝐫)c_f(\mu +M+M^{},𝐫)^{}r_MC(121;\mu ,M+M^{}),`$ (C55)
where we used

$`J=1;J_z=M|T_2^L(𝝆)|J=1;J_z=M^{}`$ $`=`$ $`{\displaystyle \frac{5}{\sqrt{8\pi }}}\delta _{M,L+M^{}}C(121;M^{},L).`$ (C56)
We have the contributions to the integrated intensity

$`I_2^{(1)}`$ $`=`$ $`I_{3}^{(1)}{}_{}{}^{}={\displaystyle 𝑑E_LS_{11;2}^{(1)}(E_L)}`$ (C57)
$`=`$ $`{\displaystyle \frac{2}{5}}\sqrt{{\displaystyle \frac{8\pi }{15}}}D_1\kappa ^2{\displaystyle \underset{if}{}}P_i{\displaystyle \underset{M,M^{}}{}}C(112;M,M^{})(1)^{M+M^{}}i|u_M^{}|ff|u_MT_2^{M+M^{}}(𝐉)|i.`$ (C58)
Here the sum over final states should be restricted to single phonon states. Higher energy states make only a small contribution to this sum. So we make the closure approximation that the sum over $`|f`$ extends over all states, in which case

$`I_2^{(1)}`$ $`=`$ $`{\displaystyle \frac{2}{5}}\sqrt{{\displaystyle \frac{8\pi }{15}}}D_1\kappa ^2{\displaystyle \underset{i}{}}P_i{\displaystyle \underset{M,M^{}}{}}C(112;M,M^{})(1)^Mi|u_M^{}^{}u_MT_2^{M+M^{}}(𝐉)|i.`$ (C59)
As illustrated by Eq. (28), the initial state $`|i`$ is dominantly comprised of a single value of $`J_z`$. Thus in Eq. C59 $`M+M^{}=0`$ dominates. In addition, the system is nearly isotropic. Then $`_MC(112;M,M)(1)^M|u_M|^2=0`$. So, to a good approximation,

$`I_2^{(1)}+I_3^{(1)}=0.`$ (C60)
We have made several approximations, but our result for the total integrated intensity will not be much affected by these approximations.

Similarly, we get

$``$ $`S_{11;4}^{(1)}(E_L)={\displaystyle \frac{16\pi }{75}}\kappa ^2D_2{\displaystyle }_{i,f,\mu ,M}P_i\delta (E_LE_f+E_i)\left|f|u_MT_2^\mu (𝐉)|i\right|^2`$ (C63)
$`{\displaystyle \frac{32\pi }{25\sqrt{21}}}D_2\kappa ^2{\displaystyle \underset{i,f,\nu ,M,M^{}}{}}P_i\delta (E_LE_f+E_i)C(112;M,M^{})C(222;M+M^{},\nu )(1)^M^{}`$
$`\times f|u_MT_2^\nu (𝐉)|if|u_M^{}T_2^{MM^{}\nu }(𝐉)|i^{}.`$
We now evaluate the integrated intensity

$`I_4^{(1)}`$ $``$ $`{\displaystyle 𝑑E_LS_{11;4}^{(1)}(E_L)}t_1+t_2,`$ (C64)
where

$`t_1`$ $`=`$ $`{\displaystyle \frac{16\pi }{75}}\kappa ^2D_2{\displaystyle \underset{i,f,\mu ,M}{}}P_ii|u_MT_2^\mu (𝐉)|ff|u_MT_2^\mu (𝐉)|i(1)^{M+\mu }.`$ (C65)
Making the closure approximation this is

$`t_1`$ $`=`$ $`{\displaystyle \frac{16\pi }{75}}\kappa ^2D_2{\displaystyle \underset{i,\mu ,M}{}}P_ii|u_Mu_MT_2^\mu (𝐉)T_2^\mu (𝐉)|i(1)^{\mu +M}`$ (C66)
$`=`$ $`{\displaystyle \frac{2}{/}}3\kappa ^2D_2{\displaystyle \underset{i}{}}P_ii|u_Mu_M|i(1)^M={\displaystyle \frac{2}{/}}3\kappa ^2D_2u^2.`$ (C67)
Similarly

$`t_2`$ $`=`$ $`{\displaystyle \frac{32\pi }{25\sqrt{21}}}D_2\kappa ^2{\displaystyle \underset{i,M,M^{}\nu }{}}P_iC(112;M,M^{})C(222;M+M^{},\nu )`$ (C69)
$`\times (1)^{M+\nu }i|u_M^{}T_2^{M+M^{}+\nu }(𝐉)u_MT_2^\nu (𝐉)|i.`$
Again, we treat $`|i`$ as having a single value of $`J_z`$, so that $`M+M^{}=0`$. Also we again assume spatial isotropy, so that $`_MC(112;M,M)(1)^M|u_M|^2=0`$. Then $`t_2=0`$.

#### d Zero Phonon Ortho Cross Section

Finally we consider the zero phonon contribution to the ortho to ortho cross section. Taking the powder average, we have

$`S_{11}^{(0)}`$ $`=`$ $`4\pi C{\displaystyle \underset{J_i=1}{}}{\displaystyle \underset{J_f=1}{}}P_i\delta (EE_i+E_f){\displaystyle \underset{\mu }{}}f|Y_2^\mu (\widehat{𝝆})|ii|Y_2^\mu (\widehat{𝝆})|f(1)^\mu .`$ (C70)
If $`\delta `$ is the energy of the $`J_z=\pm 1`$ levels relative to the $`J_z=0`$ level and if the Boltzmann probability of the state $`|m>`$ is $`P_m`$, then we may write

$`S_{11}^{(0)}`$ $`=`$ $`4\pi CP_0\delta (E+\delta ){\displaystyle \underset{m=\pm 1}{}}\left[|m|Y_2^1(\widehat{𝝆})|0|^2+|m|Y_2^1(\widehat{𝝆})|0|^2\right]`$ (C72)
$`+4\pi C\delta (E\delta ){\displaystyle \underset{m=\pm 1}{}}P_m\left[|m|Y_2^1(\widehat{𝝆})|0|^2+|m|Y_2^1(\widehat{𝝆})|0|^2\right],`$
which gives

$`S_{11}^{(0)}`$ $`=`$ $`{\displaystyle \frac{6}{/}}5CP_0\delta (E+\delta )+{\displaystyle \frac{6}{/}}5CP_1\delta (E\delta ).`$ (C73)
The ratio of cross sections at energy gain to those of energy loss does satisfy detailed balance because within the species $`(J=1)`$ we do maintain thermal equilibrium.

### 3 INTENSITY RATIOS

We develop an expression for the ratio, $`r_P`$, defined to be the integrated intensity due to phonon creation divided by that due to para-ortho conversion. Using the results for $`I^{(n)}`$ obtained above we have

$`r_P`$ $`=`$ $`{\displaystyle \frac{x𝑑E_LS_{11}^{(1)}(E_L)}{(1x)𝑑E_LS_{01}^{(0)}(E_L)}}={\displaystyle \frac{x[I_1^{(1)}+I_4^{(1)}]}{(1x)I^{(0)}}}`$ (C74)
$`=`$ $`{\displaystyle \frac{\frac{1}{/}3\kappa ^2u^2D_0+\frac{2}{/}3\kappa ^2u^2D_2}{3A}}\left({\displaystyle \frac{x}{1x}}\right)`$ (C75)
$`=`$ $`{\displaystyle \frac{2}{/}}27\kappa ^2u^2{\displaystyle \frac{j_0(\frac{1}{/}2\kappa \rho )^2+2j_2(\frac{1}{/}2\kappa \rho )^2}{j_1(\frac{1}{/}2\kappa \rho )^2}}\left({\displaystyle \frac{x}{1x}}\right).`$ (C76)
The ratio $`r_C`$, defined to be the ortho to para conversion cross section in energy gain to that in energy loss due to para to ortho conversion, is given by

$`r_C`$ $`=`$ $`{\displaystyle \frac{x}{1x}}.`$ (C77)
Finally, we have $`r_{J=1}`$, defined to be the total cross section (counting both energy loss and energy gain) for transitions within the $`J=1`$ ground manifold divided by that due to para to ortho conversion, as

$`r_{J=1}=\left({\displaystyle \frac{x}{1x}}\right){\displaystyle \frac{\frac{6}{/}5C(P_0+P_1)}{3A}}=(P_0+P_1)r_{J=1}(T=0),`$ (C78)
where

$`r_{J=1}(T=0)=\left({\displaystyle \frac{x}{1x}}\right){\displaystyle \frac{4j_2(\frac{1}{/}2\kappa \rho )^2}{15j_1(\frac{1}{/}2\kappa \rho )^2}}.`$ (C79)


text:
# Conformal fixed point, Cosmological Constant and Quintessence

\[

## Abstract

We connect a possible solution for the “cosmological constant problem” to the existence of a (postulated) conformal fixed point in a fundamental theory. The resulting cosmology leads to quintessence, where the present acceleration of the expansion of the universe is linked to a crossover in the flow of coupling constants.

\]

Once upon a time gravity was a strong force, with Newton’s constant $`G_{eff}^{(i)}=10^{110}m^3kg^1s^2`$ or effective Planck mass $`\overline{M}^{(i)}=210^{33}eV`$, and typical particle masses $`\overline{M}^{(i)}`$. The mysterious homogeneous dark energy in the universe (”cosmological constant”) started out with a similar characteristic magnitude $`V^{(i)}(\overline{M}^{(i)})^4`$. Over the ages of the history of the universe the Planck mass increased and reaches today the value $`\overline{M}^{(0)}=2.4410^{18}GeV`$. In the later stages of cosmology the mass ratios $`M_W/\overline{M}`$ and $`m_p/\overline{M}`$ for the Fermi scale and the proton mass have been approximately time independent. The growth rate of the dark energy was slower, however, such that today $`V^{(0)}=(2.210^3eV)^4`$, explaining one of the smallest numbers observed in nature, $`V^{(0)}/\overline{M}^4=6.510^{121}`$. In the present epoch the pace of change of the fundamental mass scales slows down considerably, resulting in an accelerated expansion of the universe. This tale of the cosmological history may seem somewhat weird at first sight - we will argue here that it could naturally be associated to the properties of a (postulated) conformal fixed point of a (still unknown) theory unifying all interactions.

Our basic assumption states that in a fundamental theory of all interactions (FT) all mass scales of particle physics are determined by a field $`\chi `$ rather than by a fundamental constant. This is common in grand unified, higher dimensional or superstring theories. Typically, $`\chi `$ is associated to a scale of transition such that for momenta $`p^2\chi ^2`$ all the modes of the FT are important - for example, the FT may be formulated in more than four spacetime dimensions - whereas for $`p^2\chi ^2`$ an effective description in terms of a four dimensional quantum field theory becomes valid. From the FT point of view the field $`\chi `$ plays the role of an effective infrared scale. Within the four dimensional description that we adopt here $`\chi `$ is a scalar field and may therefore evolve over cosmological time scales. In particular, the effective Planck mass is proportional to $`\chi `$. If $`\chi `$ changes with time one is led to cosmologies with a variable Planck mass .

Dilatation or scale transformations correspond to a multiplicative rescaling $`\chi c\chi `$, with constant $`c`$ and appropriate scaling of the metric and other fields. A nonvanishing cosmological value $`\chi (t)`$ “spontaneously breaks” dilatation and conformal symmetries and induces masses for most particles. If dilatation symmetry were an exact symmetry of the effective action the value of $`\chi `$ would not be an observable quantity. However, in quantum theories it is common that dilatation symmetry is violated , . by the effects of fluctuations, resulting in “running” dimensionless couplings depending on $`\chi `$. We assume that by dimensional transmutation this introduces an intrinsic scale $`m`$ in the effective potential for the cosmon field $`\chi `$, in anlogy to the characteristic scale of strong interactions, $`\mathrm{\Lambda }_{QCD}`$.

As an example, we realize these ideas in an effective model for gravity and the cosmon field $`\chi `$, characterized by an effective action $`S`$ after “integrating out” the other fields and all quantum fluctuations

$`S`$ $`=`$ $`{\displaystyle }d^4x\sqrt{g}\{{\displaystyle \frac{1}{2}}\chi ^2R`$ (2)
$`+{\displaystyle \frac{1}{2}}(\delta \left({\displaystyle \frac{\chi }{m}}\right)6)^\mu \chi _\mu \chi +V(\chi )\}.`$
Here we consider the case where for $`m0`$ the effective potential has a flat direction, and assume that for large $`\chi `$ the leading manifestation of the dilatation anomaly for $`V`$ results in a mass term

$$V=m^2\chi ^2.$$
(3)
In the region of large $`\chi m`$ all interactions are derivative interactions. The dimesionless coupling $`\delta >0`$ governs the cosmon kinetic term. The additive constant is chosen such that the model exhibits an exact local conformal symmetry $`g_{\mu \nu }c^2(x)g_{\mu \nu },\chi c(x)\chi `$ for $`\delta =0,m=0`$. In our normalization $`\chi `$ corresponds to the effective reduced Planck mass, $`\overline{M}=(8\pi G_{eff})^{1/2}`$.

It is straightforward to solve the field equations for this model  for a homogeneous and isotropic metric and cosmon field. One finds that the cosmon field increases for large time! This is due to its coupling to gravity and contradicts the too naive expectation that the cosmon should approach the potential minimum at $`\chi =0`$. The increase of $`\chi `$ has a striking consequence for the fate of the homogeneous dark energy. Indeed, only mass ratios are physically observable . For the effective “cosmological constant” $`V/\overline{M}^4`$ we find that $`V^{1/4}`$ increases less rapidly than $`\overline{M}=\chi `$. Therefore the dark energy vanishes asymptotically if $`\chi `$ increases with time, i. e. $`V/\overline{M}^4=m^2/\chi ^20`$. This is the basic ingredient for our explanation  why the “cosmological constant” vanishes asymptotically and why dark energy has attained an extremely small value today as a consequence of the enormous age of our universe.

Before we can proceed to a quantitative discussion of cosmology we need to specify $`\delta (\chi /m)`$. For large $`\chi m`$ simple dimensional arguments tell us that the $`\chi `$-dependence can be written in terms of a “renormalization group equation” $`\delta /\mathrm{ln}\chi =\beta _\delta (\delta )`$. A computation of $`\beta _\delta `$ would need the knowledge of the FT since the dominant contributions arise from modes with $`p^2\chi ^2`$. We only know that $`\beta _\delta `$ should have a zero for $`\delta =0`$, since $`\delta =0`$ corresponds to an enhanced (conformal) symmetry and separates a stable model for $`\delta 0`$ from an unacceptable unstable model for $`\delta <0`$. By continuity, for small enough $`\delta `$ the $`\beta `$\- function is also small and $`\delta `$ increases only slowly with $`\chi `$ (assuming $`\beta _\delta 0`$). For $`\chi `$ varying over many orders of magnitude during the cosmological evolution we may nevertheless be confronted with a situation where $`\delta `$ has grown large at some critical value $`\chi _c`$. At this scale we expect a crossover from the vicinity of the conformal fixed point at $`\delta =0`$ to an unknown behavior for large $`\delta `$. The crossover scale $`\chi _c`$ can play an important role in cosmology. In particular, we will discuss a scenario where $`\chi `$ reaches $`\chi _c`$ in the present epoch, triggering an accelerated expansion of the universe .

As a simple example we take

$$\frac{\delta }{\mathrm{ln}\chi }=\beta _\delta =E\delta ^2,\delta =\frac{1}{E\mathrm{ln}(\chi _c/\chi )},$$
(4)
where $`\chi _c`$ depends on $`E`$ and the “initial value” $`\delta _i=\delta (\chi =m)`$. For small $`E\delta _i`$ the separation between the crossover scale $`\chi _c`$ and the intrinsic scale $`m`$ becomes exponentially large

$$\frac{\chi _c}{m}=\mathrm{exp}\left(\frac{1}{E\delta _i}\right),$$
(5)
in close analogy to the inverse ratio between the strong interaction scale $`\mathrm{\Lambda }_{QCD}`$ and the unification scale. In particular, if $`\chi _c`$ is associated to the present value $`\overline{M}^{(0)}=\overline{M}_p=2.4410^{18}GeV`$ and $`E\delta _i1/138`$ we obtain a present value for the potential part of the dark energy

$`V^{(0)}`$ $`=`$ $`m^2\chi _c^2=\mathrm{exp}\left({\displaystyle \frac{2}{E\delta _i}}\right)\overline{M}_p^4`$ (6)
$`=`$ $`6.5610^{121}\overline{M}_p^4=(2.210^3eV)^4.`$ (7)
We emphasize that the cosmological evolution for this class of models is independent of the initial conditions since the late time behavior is governed by a cosmic attractor solution . Generically, the ratio $`\mathrm{\Omega }_h`$ between the homogeneous dark energy density and the critical energy density stays small as long as $`\delta `$ is small, adjusting itself to a dominant radiation or matter component, $`\mathrm{\Omega }_h\delta `$ or $`\mathrm{\Omega }_h\frac{3}{4}\delta `$, respectively. This behavior only changes once $`\chi `$ reaches the crossover scale $`\chi _c`$, and for $`E\delta _i1/138`$ this happens precisely at the present epoch. Then the universe switches to a regime where dark energy dominates.

To be more quantitative we select***We have divided $`\beta _\delta `$ in eq.(4) by $`(1+0.05\delta )`$ in order to keep $`\delta `$ finite for all $`\chi `$, without affecting the behavior for small and intermediate $`\delta `$. $`E=5,\delta _i=1.44410^3`$. We can now compute the characteristic quantities like the amount of dark energy today, $`\mathrm{\Omega }_h^{(0)}=0.7`$, or the equation of state $`w_h=p_h/\rho _h`$ at the present time, $`w_h^{(0)}=0.93`$. They are compatible with the supernovae observations  and the age of the universe $`t^{(0)}=13.710^9yr`$. For a discussion  of the spectrum of the CMB-unisotropies we need, in addition, the value of $`\mathrm{\Omega }_h^{(ls)}=0.019`$ at the time of last scattering and an averaged equation of state $`\overline{w}`$ which determine the position of the third peak in angular momentum space as $`l_3=795`$ (for $`h=0.66)`$. Structure formation is slowed down by the early presence of dark energy . It depends on an average of $`\mathrm{\Omega }_h`$ over the time of structure formation, $`\mathrm{\Omega }_h^{(sf)}=0.037`$ . In our case the cold dark matter density fluctuations are reduced by a factor $`\sigma _8/\sigma _8(\mathrm{\Lambda })=0.7`$ as compared to a model with a cosmological constant and the same amount of dark energy today. We conclude that our simple model is compatible with the present observations. We observe interesting differences as compared to models with a cosmological constant. They are subject to future observational tests.

Several comments are in order: (i) Cosmology is most easily discussed after a Weyl scaling $`g_{\mu \nu }(\overline{M}_p/\chi )^2g_{\mu \nu }`$ and a redefinition of the cosmon field $`\phi /\overline{M}_p=\mathrm{ln}\left(\chi ^4/V(\chi )\right)=2\mathrm{ln}(\chi /m)`$, such that the coefficient in front of the curvature scalar $`R`$ becomes constant and $`\phi `$ is directly related to the value of the potential

$`S`$ $`=`$ $`{\displaystyle }d^4x\sqrt{g}\{{\displaystyle \frac{1}{2}}\overline{M}_p^2R`$ (9)
$`+{\displaystyle \frac{1}{2}}k^2(\phi )^\mu \phi _\mu \phi +\overline{M}_p^4\mathrm{exp}({\displaystyle \frac{\phi }{\overline{M}_p}})\}.`$
The details of the model are now encoded in the nontrivial kinetic term  $`k^2(\phi )=\delta /4`$. As a general feature, the motion of the cosmon slows down once $`k^2`$ becomes large, in our case for $`\phi `$ near $`\phi _c=2\overline{M}_p/(\delta _iE)`$. Then the dominance of the potential $`V`$ over the kinetic energy $`T`$ leads to a negative equation of state $`w_h=(TV)/(T+V)`$ and to an acceleration of the universe .

ii) The qualitative features of our proposal hold for a much more general class of cosmon potentials $`V`$. For example, adding to eq. (3) a “bare cosmological constant” $`\gamma m^4`$ becomes completely irrelevant for large $`\chi /m`$. Only the behavior of $`V`$ for large $`\chi `$ matters. The scenario of an asymptotically vanishing dark energy holds provided that $`V`$ increases less rapidly than $`\chi ^4`$ and $`\delta `$ remains finite for $`\chi <\overline{M}_p`$. This applies, in particular, to an asymptotic behavior $`V=\lambda (\chi /m)\chi ^4`$ with a dimensionless coupling $`\lambda `$ obeying the renormalization group equation

$$\frac{\lambda }{\mathrm{ln}\chi }=A\lambda ,A>0.$$
(10)
iii) Details of cosmology depend on $`\beta _\delta `$. For $`\beta _\delta =0`$ one recovers “exponential quintessence” , whereas for $`\beta _\delta =D\delta ,D`$ constant, one finds “inverse power law quintessence”  with power $`\alpha =2A/D`$. We have studied other models with crossover behavior, e. g.: $`\beta _\delta =D\delta +E\delta ^2`$. For $`D>0`$ the required value of $`\delta _i`$ decreases and early quintessence (e. g. $`\mathrm{\Omega }_h^{(ls)},\mathrm{\Omega }_h^{(sf)})`$ becomes less important. The precise flow for very large $`\delta `$, i. e. $`\delta `$ remaining finite for all $`\chi `$, plays only a minor role for presently observable cosmology provided $`\delta `$ grows sufficiently large in the present epoch.

iv) We can extend our description to matter fields and radiation. As an example we consider the Higgs doublet $`H`$, a fermion field $`\psi `$ and the gluons characterized by their field strength $`F_{\mu \nu }`$. Within our assumption this adds to eq. (2) a term

$`S_M={\displaystyle }d^4x\sqrt{g}\{(\lambda _H/2)(H^{}H\beta ^2\chi ^2)^2`$ (11)
$`+(h\overline{\psi }_LH\psi _R+h.c.)+{\displaystyle \frac{Z_F}{4}}F^{\mu \nu }F_{\mu \nu }\}.`$ (12)
Our previous description has neglected the possible $`\chi `$-dependence of the dimensionless couplings $`\lambda _H,\beta ,h,Z_F`$ such that after the Weyl scaling $`\phi `$ decouples completely from matter and radiation. In this case the Higgs doublet reaches its $`\chi `$\- dependent minimum $`|H|^2=\beta ^2\chi ^2`$ early in cosmology (after the electroweak phase transition). Similarly, for a fixed value of the running gauge coupling at some grand unified scale $`M_X,\alpha _S(M_X)1/40`$, we find $`\mathrm{\Lambda }_{QCD}\chi `$ if $`M_X\chi `$. In this approximation all ratios of particle masses become independent of $`\chi `$ and do not vary with cosmological time.

We note the appearance of two different types of characteristic masses for the excitations. The excitation along the “vacuum direction” corresponds to a simultaneous change of all mass scales (along the direction $`|H|=\beta \chi )`$. Its mass is given by the small intrinsic mass $`m`$. On the other hand, the excitations perpendicular to the “vacuum direction” correspond to a variation of mass ratios and have a characteristic mass $`\chi `$. In our example, the intrinsic mass $`m`$ is many orders of magnitude smaller than the (present) mass of the Higgs boson $`M_H^2=\lambda _H\beta ^2\chi ^2`$. This resembles the spontaneous breaking of some unknown global symmetry where a small mass $`m`$ for the pseudo-Goldstone boson $`\chi `$ is induced by an anomaly.

v) We do not expect the dimensionless couplings $`\lambda _H,\beta ,h,Z_F`$ to be precisely independent of $`\chi /m`$. Then the cosmological variation of $`\chi /m`$ will induce a time dependence of the fundamental parameters. Severe bounds  restrict  this dependence for the dimensionless couplings of the known fields. More freedom is left for a coupling of the cosmon $`\phi `$ to dark matter- sizeable couplings would influence the cosmology . Very close to the big bang, for $`\chi m`$, the dependence of all couplings on $`\chi /m`$ may have been strong.

vi) In a grand unified theory the renormalized strong gauge coupling or the fine structure constant $`\alpha _{em}`$ depend on the value of the gauge coupling $`g_X=g(M_X)`$ at the unification scale $`M_X`$ where $`g_X^2(\chi )Z_F^1(\chi )`$. We neglect here for simplicity the $`\chi `$-dependence of $`M_X,B_X=\mathrm{ln}(M_X/\chi )/\mathrm{ln}\chi 0`$, and concentrate on the case where for $`\chi \mathrm{}`$ the running of $`g_X`$ is governed by a fixed point $`g_{}^2/4\pi 1/40`$

$`{\displaystyle \frac{g_X^2}{\mathrm{ln}\chi }}=\beta _{g^2}`$ $`=`$ $`b_2g_X^2b_4g_X^4,`$ (13)
$`b_2`$ $`=`$ $`b_4g_{}^2>0.`$ (14)
It is interesting to associate $`m`$ with the nonperturbative scale where $`g_X(\chi m)\mathrm{},`$

$$g_X^2=g_{}^2\left[1\left(\frac{\chi }{m}\right)^{b_2}\right]^1.$$
(15)
The present relative variations of the gauge couplings are then determined by

$`\eta _F={\displaystyle \frac{\beta _{g^2}}{g_X^2}}b_2\left({\displaystyle \frac{\chi }{m}}\right)^{b_2}=\mathrm{exp}\left({\displaystyle \frac{b_2\phi }{2\overline{M}_p}}\right).`$ (16)
For sufficiently large $`b_2`$, say $`b_2>0.2`$, the time variation of $`\mathrm{\Lambda }_{QCD}`$ or $`\alpha _{em}`$ is much too small to be accessible for present observations . More generally, we conclude that a fixed point which is approached sufficiently fast for $`\chi \mathrm{}`$ could give a very simple explanation why the cosmological time variation of fundamental couplings is small. On the other hand, the substantial variation of $`\delta `$ at the present cosmological epoch may have a small influence on the precise location of the fixed point $`g_{}(\delta )`$. A small increase of $`g_{}(\delta )`$ can lead to a time variation of $`\alpha _{em}`$ in the range inferred from the observation of quasar absorption lines , corresponding to $`\eta _F=410^7`$. Recent investigations indeed show  that a small $`\delta `$-dependence of $`\beta _{g^2}`$ makes the QSO observation compatible with all present bounds from archeo-nuclear physics and tests of the equivalence principle, provided that the crossover is sufficiently rapid (e.g. $`E=8`$).

vii) The effect of the quantum fluctuations is encoded in the $`\beta `$-functions (10), (13). In our setting this concerns mainly small deviations from a conformal fixed point at $`\delta =0,\lambda =0,g^2=g_{}^2`$. We emphasize that the existence of a fixed point at $`\lambda =0`$ seems plausible since it separates again a stable $`(\lambda >0)`$ from an unstable $`(\lambda <0`$, unbounded potential) situation.

The conformal fixed point has $`g^2`$ (and $`\lambda `$) as relevant coupling for $`\chi 0`$ whereas for $`\chi \mathrm{}`$ the relevant coupling corresponds to $`\delta `$. The flow of the couplings is therefore neither stable towards the infrared nor towards the ultraviolet. The scale $`m`$ marks the first infrared scale where couplings grow large (e. g. the gauge coupling) whereas $`\chi _c`$ corresponds to the instability in the ultraviolet. A huge ratio $`\chi _c/m`$ occurs whenever the trajectory of the flow passes sufficiently close to the fixed point.

A crucial question concerns the running of $`\lambda `$ for large $`\chi `$ which can depend on the various dimensionless couplings $`\lambda /\mathrm{ln}\chi =\beta _\lambda (\lambda ,\delta ,g^2,h,\lambda _H,\mathrm{}).`$ Near a fixed point with only one relevant (marginal) coupling $`(\delta )`$ all couplings follow critical trajectories which may be parameterized by $`\delta (\lambda ),g^2(\lambda ),h(\lambda )`$ etc. Inserting these functions into $`\beta _\lambda `$ yields an expansion for small $`\lambda ,\beta _\lambda =c_\lambda A\lambda +\mathrm{}`$. Only for $`c_\lambda =0`$ the fixed point occurs for $`\lambda _{}=0`$ and only in this case the effective cosmological constant vanishes asymptotically. Our assumption of a flat direction in the effective cosmon potential is equivalent to $`c_\lambda =0`$. The individual contribution of a particle with mass $`M_j=\gamma _j\chi `$ is $`c_\lambda \gamma _j^4`$. Even though $`\gamma _j`$ is a tiny coupling for standard model particles the resulting cosmological constant would come out much too large $`(M_j^4)`$, reflecting the “naturalness” or “fine tuning” problem.

It is obvious, however, that $`c_\lambda `$ will be dominated by the unknown particles with mass around $`\chi `$. From the point of view of the low energy theory the value of $`c_\lambda `$ is an ultraviolet problem. We see no way to make statements about the location of $`\lambda _{}`$ from our knowledge of the low energy theory The situation is very different if the location of a fixed point is dominated by the infrared modes! Actually, an attempt to characterize the location of an ultraviolet fixed point by the couplings of the infrared modes would be similarly misleading as the characterization of an infrared fixed point by properties of the ultraviolet modes.. This argument is strengthened if $`\gamma _j`$ depends on $`\chi `$ as in our setting. In this case even the contribution of the low mass particles to $`c_\lambda `$ is not uniquely dominated by momenta $`q^2M_j^2`$ \- it also involves “ultraviolet momenta” $`q^2\chi ^2`$. We think that in view of this situation our conjecture that $`V(\chi )`$ rises for large $`\chi `$ less rapidly than $`\chi ^4`$ (coresponding to $`\lambda _{}=0)`$ seems to be a reasonable possibility Our setting circumvents an argument  that time varying fundamental constants require the tuning of a whole function. Only $`c_\lambda =0,A>0`$ is required.. In this respect it is crucial that the late time behavior explores the ultraviolet rather than the infrared!

We conclude that in a fundamental theory the presence of a conformal fixed point with a flat direction, together with the flow of small deviations from the fixed point proposed in this note $`(A>0)`$, would lead to a natural explanation why the cosmological constant vanishes for asymptotic time. After Weyl scaling, no additive constant hinders the asymptotic approach of the cosmon potential to zero, $`V(\phi \mathrm{})0`$. This would solve the “cosmological constant problem” . In our crossover scenario the past evolution of the universe is characterized by a small and slowly varying fraction of dark energy which adapts to a dominant radiation (matter) component $`\mathrm{\Omega }_h\delta \left(\frac{3}{4}\delta \right)`$. The future of the universe depends crucially on the unknown properties of the flow of $`\delta (\chi )`$ in the region of the large $`\delta `$. The present epoch witnesses a crossover from small to large $`\delta `$, resulting in an accelerated expansion. In a FT the crossover scale $`\chi _c/m`$ should be computable, just as the values of mass ratios or dimensionless couplings in particle physics. It is therefore not excluded that some of the “cosmic coincidences” (relations between the present value of the Hubble parameter $`H_0`$ and particle properties) could find an explanation in this direction. For the potential (3) the present value of $`H`$ is given by the mass $`m`$ characterizing the dilatation anomaly

$$H_0^2=\frac{2\mathrm{\Omega }_h^{(0)}}{3(1w_h^{(0)})}m^2.$$
(17)
The time variation of the dark energy could be detected by cosmological observations in the near feature, and an establishment of a time variation of fundamental couplings would be a striking argument in favor of our proposal.