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# Sound modes broadening in quasicrystals.

## I Introduction

In most many body systems there is a fairly sharp distinction between elementary excitations (quasi - particles) and the collective modes involving a coherent mixture of quasi - particles. In a harmonic dielectric crystal these elementary excitations are phonons, having the linear dispersion law. At finite temperatures $`T`$ the great majority of phonons have energies at most of the order of $`T`$ due to the nature of the Bose - Einstein distribution, and the thermodynamic properties of crystals are determined almost entirely by these excitations. The wave vector associated with a phonon in a regular lattice is only defined modulo a reciprocal lattice vector, a feature which plays a crucial role in the dynamical properties of crystals. In this respect phonons in crystals are quite different from sound waves in liquids which carry true momentum. Each atom in the crystalline lattice executes only a finite amplitude motion (the oscillation about the lattice site). Evidently the mean momentum of such a motion is identically zero, and therefore the phonon flux associated with the energy flux in a crystal is not accompanied by a transfer of mass.

QC systems are quite different from conventional solid crystals. QCs are built roughly speaking according to the following principles: being homogeneous like crystalline alloys QCs nevertheless posses specific structural elements, or clusters (see rev1 , mon1 , mon2 ). The resulting construction has no translational symmetry but has long-range order. In spite of the fact that QC systems do not show lattice periodicity, the above statement on zero mean momentum of phonons should be true for QCs also. Thus one must admit that phonons in QC systems carry not momentum but only quasi - momentum, which is defined, unlike in conventional crystals, modulo a dense set of reciprocal vectors KC96 . Both systems (crystals and QCs) in this respect are different from liquids, where the phonon momentum is the actual momentum and the phonon flux does involve a transfer of mass, since in a sufficiently long time any atom or molecule can reach any point in the volume.

Thus one could say that i-QCs are quasicrystalline on the near atomic scale, and isotropic solids at macroscopic scales. Somewhere there ought to be a crossover from the local arrangement to macroscopic isotropy. If this structural crossover is sufficiently abrupt, it might also mark in reciprocal space the upper frequency end of the isotropic acoustic branches. Besides, because QC systems do not show lattice periodicity, the concept of Brillouin zone and its use for characterizing elementary excitations like phonons, strictly speaking is not adequate JA00  (see also KL03 , SR03 ). On the other hand, at least at first glimpse, it can be argued that because in the long - wavelength limit the phonons can be described as sound waves propagating through an elastic continuum, there should be little difference between QCs and crystalline materials in this regime where the phonons are insensitive to microscopic structure. Nevertheless, experimental results are fairly different in the two types of systems. The following correlation is characteristic of classical mono-crystals: the higher the quality of the diffraction pattern of a mono-crystal, the lower the line-widths of the phonons. The correlation reflects the wave nature of phonons: the better the conditions for the propagation, the smaller the scattering of the Bloch-type waves. Since QCs do not posses lattice periodicity vibrational excitations QCs are intrinsically not Bloch-type eigen-modes and therefore this correlation does not hold.

The same kind of problem has been discussed in the literature on electronic excitations in QCs. Some unusual electronic properties (e.g. a very low value of the electrical conductivity, a negative temperature coefficient of the resistivity, and so on) as it was shown recently RM97  are the consequences of the spectral properties of quasiperiodic Hamiltonians. It is common knowledge now that Anderson localization AN84  is a second - order phase transition between eigenstates that are spatially localized and those that are delocalized, and there are well defined conditions at which the localization - delocalization transition occurs. Many numerical investigations of quasiperiodic Hamiltonians reveal that their eigenstates are critical, i.e. they are characterized by a power-law decay of the amplitudes (see JA96 , FM96 ). The existence of the critical electronic states can be understood as related to the self-similarity of the QC structures: a given atomic cluster is repeated within a distance of the order of its size, and therefore an eigenstate from any cluster can easily tunnel to the next one which has an identical form. Thus electronic properties of QCs are critical, at least from the point of view of the second order Anderson localization - delocalization transition.

However this analogy can not be bluntly applied to the study of vibrational modes in QCs. There are two principal differences between the Anderson electron and the vibrational problems, which are our main concern here. Firstly, when the system is mechanically stable, there are no negative eigenvalues (unlike in the electron case). Secondly in the 3d vibrational case, there are always at least 3 zero - frequency (in the long wavelength limit) Goldstone modes that can not be localized. Therefore, since the modes at the lower energy bound of the spectrum must have extended character, one can expect something similar to critical states (and to localization - delocalization transitions) only near the relatively high - frequency band edge.

The issue (elementary vibrational excitations in QCs) was intensively studied recently, and inelastic neutron scattering data (see e.g. DB99  \- SK02 , rev1 , HK93  and the monographs mon1 , mon2 ) reveal in the long wavelength limit well defined acoustic modes. The experimental quantity investigated in these experiments, the so - called scattering function $`S(𝐐,\omega )`$, is measured close to a Bragg reflection located at a certain reciprocal vector $`𝐆`$ in momentum space, and it probes phonons with frequency $`\omega `$ and wave vector $`𝐪=𝐆𝐐`$. To measure the largest signal one should measure $`S(𝐐,\omega )`$ at high momentum transfer and close to a strong Bragg peak. Neutron scattering investigations were performed for different icosahedral DB99  \- CO98 , and decagonal SK02  structures and it turned out that in spite of the fact that, structurally, decagonal and icosahedral QCs are rather different, and that their physical properties (e.g. elastic moduli) might be also very different, they exhibit many common vibrational features. The purpose of our paper is to propose a simple phenomenological model to try to obtain as much theoretical information concerning vibrations in QCs as is possible on a phenomenological level without specific microscopic treatment. The rest of the paper is organized as follows: in Section II we give a short outline of neutron data related to vibrational mode studies in i-QCs $`AlPdMn`$ and $`ZnMgY`$. Section III is devoted to the description of our phenomenological model. Finally, Section IV deals with miscellaneous subjects related to the vibrational dynamics in QCs.

## II Experimental overview

The excitation spectrum of different QCs has been studied by inelastic neutron scattering on single grain samples. In spite of the often contradictory results of experimental investigations (see e.g. discussions in SF02 , SL02 ), a few conclusions listed below seem inescapable. As explained above, it is only in the acoustic regime that a one to one correspondence can be made between the observed signal and a phonon, i.e. that the phonon wave vector can be defined. Generally, results are presented in an ’extended’ zone scheme, with a strong Bragg peak acting as the zone centre (for crystallographic details see e.g. CS86 ). As proposed by Niizeki, NI89 , NA90  important pseudo Brillouin zone boundaries (PZB) can be defined. They correspond to strong Fourier components of the atomic density from which acoustic modes are Bragg reflected. The positions of these pseudo zone boundaries obviously depend on the details of the atomic structure. Moreover, because of the quasi periodicity, several successive PZBs are stacked around each strong zone centre.

In the following we will focus on two icosahedral phases for which detailed studies have been carried out: $`iAlPdMn`$ and $`iZnMgY`$ . These two icosahedral phases have a very different atomic structure. Nevertheless their excitation spectra share a lot of common features. Their dynamical response can be separated into two well defined regimes: the acoustic regime for wave vectors smaller than $`0.6\AA ^1`$, and, for larger wave vectors, a regime in which the dynamical response is characterised by a broad band of dispersionless optic-like modes. In the acoustic regime, excitations are generally resolution limited for $`q`$ smaller than $`0.3\AA ^1`$, and then broaden.

The way in which the broadening develops strongly depends on the atomic structure of the icosahedral phase: for instance it is much more rapid in the $`iAlPdMn`$ phase than in the $`iZnMgY`$ phase. The optic like spectrum generally consists of 3 or 4 broad ’bands’ (a few $`meV`$ wide) around 7, 12, 16 and 24 $`meV`$. Although no gap opening could be observed at the PZBs, the energy of the lower optical modes roughly corresponds to the intersection of the acoustic branch with the PZBs.

Figure 1 summarises results obtained for transverse modes propagating along a 2-fold axis and polarised in a 2-fold direction. The upper part is for the $`iAlPdMn`$ phase and the lower one for the $`iZnMgY`$ one. The transverse acoustic phonon dispersion relation is given by the full circles. The dashed line is the corresponding sound velocity as extracted from ultrasonic measurements. The open circles correspond to the width of the $`TA`$ modes. The other open symbols correspond to the different broad optic ’bands’, whose width is of the order $`4meV`$. For both phases the crossover between the acoustic and, say, hybridized regime is fairly abrupt: for the $`iAlPdMn`$ phase it shows up as a rapid broadening of the $`TA`$ acoustic mode, whereas for the $`iZnMgY`$ there is a coupling with an optic like excitation localised at $`10meV`$. In both cases the $`TA`$ limit is given by $`q=0.6\AA ^1`$. Above this value the $`TA`$ acoustic mode mixes up with optical excitations and the observed signal can no longer be described as a single excitation.

The broadening of $`TA`$ excitations also depends on the structure: it is about two times larger in the $`iAlPdMn`$ phase than in the $`iZnMgY`$ one. From the local slope of the $`TA`$ dispersion relation and width of the excitations it is also interesting to compute the mean free path of $`TA`$ phonons at the upper limit of the acoustic regime. We find a mean free path of $`12\AA `$ and $`24\AA `$ for the $`iAlPdMn`$ and $`iZnMgY`$ phases, respectively. Structural X-ray studies SF98  have shown one special geometric aspect of all QC structures, namely, atomic clusters, with a characteristic diameter $`D_{cl}=10\AA `$, which are part of the building blocks of QCs and their close approximants. Summarising the experimental dynamics study, we can thus say that the crossover between the acoustic and mixed regime occurs for a phonon wavelength equal to $`D_{cl}`$. The mean free path of the $`TA`$ phonon is equal to $`D_{cl}`$ and $`2D_{cl}`$ for the $`iAlPdMn`$ and $`iZnMgY`$ phases, respectively.

Line broadening is a nuisance in some circumstances, while in our case of QCs it provides valued physical information. We show in Fig. 2 dependences of line width for longitudinal (the upper panel) modes propagating along a 5-fold axis and for the transverse modes (the lower panel) propagating along a 2-fold axis in the $`iZnMgY`$ phase, and the width for the transverse mode propagating along a 2-fold axis for $`iAlPdMn`$ is shown in Fig. 3. The instrumental width for longitudinal modes (about 2 mev) is larger than for transverse (about 1 mev). To gain further insight into the nature of broadening we show in Figs. 2 and 3 theoretical fitting by $`q^2`$ dependence for the longitudinal waves and by $`q^4`$ for the transverse modes. We will see in the next section that these dependences correspond to broadenings dominated respectively by Akhiezer and by resonance hybridization sound absorption.

It is worth noting that very similar results are obtained for physically and structurally very different systems like i-QC $`CdYb`$ or decagonal - QC $`AlNiCo`$ (see DB99  \- SK02 ). Even numerical values for the acoustic line-width cross-over are not very different, however, to be specific we restrict ourselves in this paper to the i-QCs $`AlPdMn`$ and $`ZnMgY`$ only for which we have more detailed and reliable data due to the high quality of the samples.

## III Phenomenological Akhiezer model

Whereas the knowledge on the sound propagation in ordered crystals or disordered glass-like structures is now rapidly improving (see e.g., CF03 , RF03 , and references therein), little is known about the behavior in systems with non-periodic long-range order, such as QCs. The general objective of this study is to determine the structural and physical mechanisms associated with phonon line broadening in order to identify those features of QCs which differentiate them from conventional crystalline systems. Since both features (characteristic clusters and almost dispersionless optical modes) are interrelated and practically ubiquitous for all QCs it is natural to look for a model based on these widely recognized specific features. The primary aim of this section is to present such a physical model that reproduces available experimental data on vibrational eigenmodes in QC. In particular we are going to consider general phenomenological processes leading to sound absorption and dispersion, as the detailed microscopic mechanisms governing these processes are not fully understood yet and have been heavily debated in the literature SF02 , SL02 .

The occurrence of many broad optical, almost dispersionless modes has been, at least qualitatively, established and their origin can be easily understood. Indeed, as is well known AM76 , the number of optical modes in a crystal is related to the number of atoms in the unit cell. Since in QC systems the unit cell size is strictly speaking infinite, it is not surprising to have in a certain energy window a dense set of optical modes. Moreover due to natural energetic restrictions the energy window where all the optical modes are confined is a relatively narrow one, which unavoidably leads to small mode dispersion. We shall thus include from the very beginning these modes into the model. On the other hand the dispersionless character of the optic modes means that the corresponding excitations see an almost uniform medium, the strain of which is slowly modulated by the sound wave. Due to the anharmonicity of the system the strain of the sound field causes a change of the optic mode frequencies. Despite the apparent analytic intractability of the problem, the various approaches suggest that all the complications can be subsumed by a simple phenomenological form.

In order for the discussion to proceed smoothly, we start first with a simple argument. We generalize to QCs the well - known Akhiezer mechanism of sound absorption (see AK39  and also BD60 ). In the case (we will be interested in below) when the frequency of the sound waves is much smaller than all relevant inverse relaxation times, the sound vibrations can be considered as a certain external field which modulates the QC structure, and therefore the optical mode frequencies

$`\omega _0^{(\alpha ,a)}=\omega _0^{(\alpha ,a)}(1+\gamma _{ij}^{(\alpha ,a)}u_{ij}),`$ (1)
where $`\alpha `$ denotes the polarization of the optic mode $`a`$, $`\gamma _{ij}^{(\alpha ,a)}`$ is the second rank tensor which characterizes the QC and depends on the direction of the optic mode $`(\alpha ,a)`$ propagation. It can be viewed as the generalized Gruneisen constant tensor (see AK39  and also BD60 ).

To simplify the matter (though it is not a crucial point) we assume that $`\gamma `$ does not depend on the frequency $`\omega `$. It can be shown using standard thermodynamic relations LL80  that in this case the optical mode frequency modulation does not disturb the thermodynamic equilibrium within this branch, thus it is still proper to attribute a temperature $`T`$ to it

$`\left({\displaystyle \frac{\mathrm{\Delta }T}{T}}\right)^{(\alpha ,a)}\left({\displaystyle \frac{\mathrm{\Delta }\omega _0}{\omega _0}}\right)^{(\alpha ,a)}.`$ (2)
This relation (2) is valid if during the strain deformation collisions with other branches can be neglected. However since for different modes the values of $`\gamma `$ can be different (even could be negative or positive), after a strain deformation each branch has in general a different temperature (some branches might be cooled down, while others are heated up).

It might be useful first to separate all optical modes into two groups with different average temperatures but comparable specific heats. The average relative temperature difference between the groups, and according to (1), (2), the average generalized Gruneisen coefficient $`\widehat{\gamma }_{\alpha \mathrm{av}}`$ can be then easily calculated. Indeed one should bear in mind that although the modes contribute additively to the free energy, the Gruneisen coefficients are determined by a ratio of derivatives, i.e. a ratio of sums

$$\widehat{\gamma }_{\alpha \mathrm{av}}=\frac{_a\widehat{\gamma }^{(\alpha a)}C_a}{_aC_a},$$

where $`C_a`$ is the specific heat associated to the mode $`a`$.

If a sound wave propagates through a system, a periodic temperature difference will be set up between the two groups. Therefore in a certain characteristic relaxation time $`\tau `$, heat exchange takes place between them, leading to entropy production, and absorption of the sound wave. The absorption coefficient per unit length $`\alpha _\alpha `$ (in $`cm^1`$) is determined by the entropy production rate and reads LL86

$`\alpha _\alpha ={\displaystyle \frac{C_\alpha T\gamma _{\alpha ,\mathrm{av}}^2}{\rho c_\alpha ^3}}{\displaystyle \frac{\omega ^2\tau }{1+\omega ^2\tau ^2}},`$ (3)
where $`C_\alpha `$ is the heat capacity at constant strain corresponding to each sound mode polarization (constant volume for longitudinal waves and constant shear for transversal ones), $`\rho `$ is the mass density, and $`c_\alpha (c_l,c_t)`$ is the longitudinal or transverse sound mode velocity.

It seems reasonable to assume that the energy exchange between the two groups takes place by means of phonon - phonon scattering processes. The relevant point is that the same kind of processes determine the heat conductivity LL81  $`\kappa `$

$`\kappa ={\displaystyle \frac{1}{3}}C_vc_l^2\tau ,`$ (4)
where $`C_v`$ is the constant-volume specific heat, and $`c_l`$ is the longitudinal mode velocity.

The expressions can be brought into more compact forms by taking into account that at high enough temperatures the relaxation time $`\tau `$ is much shorter than the sound period. Comparing (3) and (4) we end up with the following coefficients for the longitudinal ($`\alpha _l`$) and transverse ($`\alpha _t`$) sound absorption

$`\alpha _l{\displaystyle \frac{\kappa \gamma _{l,av}^2}{\rho c_l^5}}T\omega ^2,`$ (5)
and

$`\alpha _t{\displaystyle \frac{\kappa \gamma _{t,av}^2}{\rho c_t^3c_l^2}}{\displaystyle \frac{C_t}{C_v}}T\omega ^2,`$ (6)
where $`C_t`$ is the heat capacity at constant shear strain.

For the benefit of the skeptical reader, some comments about the applicability of the mechanism described in this section to transverse modes, seem in order. Indeed conventional wisdom claims that the Akhiezer mechanism cannot be applied directly to transverse sound modes, since only dilatation or compression deformations may provide non - uniform temperature variations and thermo-diffusive dissipation. To resolve the contradiction we should recall that the building blocks of all QC structures are atomic clusters. These clusters are not mere geometrical constructions but real physical entities responsible for specific features in the QC vibrational spectrum (e.g., responsible for localized modes). Hence, one expects acoustic vibrations to induce stress inhomogeneities around each cluster, with a resulting strain field that will consist of a superposition of a dilation and of a shear.

Therefore in this case the internal thermoelastic dissipation occurs even for the pure transverse vibrations. It is reminiscent of a phenomenon known in classical elasticity theory LO44  whereby a spherical inclusion placed in a vibrating medium containing only pure shears, introduces local strains which have dilation $`\mathrm{\Delta }(r,\theta ,\varphi )`$ ($`r`$, $`\theta `$, and $`\varphi `$ are spherical coordinates) proportional to the shear deformation $`s`$ at large distances from the inclusion

$`\mathrm{\Delta }=s\left({\displaystyle \frac{5\mu }{9\lambda +14\mu }}\right)\left({\displaystyle \frac{D_{cl}}{r}}\right)^2\mathrm{sin}^2\theta \mathrm{cos}\varphi \mathrm{sin}\varphi ,`$ (7)
where, for an isotropic material, $`\mu `$ and $`\lambda `$ are the only two non-zero elastic constants. To find Akhiezer line broadening following from the dilation (7) one should calculate and average the corresponding Gruneisen coefficient. For one spherical inclusion in a bulk isotropic material the total effect will be zero due to angular integration. But of course this picture of one isolated cluster in a vibrating medium is not adequate for QC clusters. A complete account of the strains induced by the sound modes in real QC structures requires considerable computational work, that is beyond the scope of our purely phenomenological model. Thus we use in (6) phenomenologically the average transverse Gruneisen coefficient $`\gamma _{t,av}`$. However from simple arguments presented above concerning the expression (7) we can come to the conclusion that due to the cluster-like nature of all QC structures, the Akhiezer broadening is expected to be less efficient for the transverse phonons than for the longitudinal ones. Therefore at least for the former case we have to look for another mechanisms contributing to transverse mode broadening in QCs.

QC clusters play also a crucial role for sound mode hybridization in QCs. Indeed, if we consider the vibrations of an isolated cluster of size $`D_{cl}`$, then the high-frequency modes with $`\lambda D_{cl}`$ will not be affected by the change in the boundary conditions at scale $`D_{cl}`$, involved in partial disconnecting the cluster from the rest of the system. On the other hand, the low-frequency modes for which $`\lambda D_{cl}`$ will disappear from the spectrum. Very qualitatively one can then think of such a material as a dense packing of connected clusters. Phonon scattering from fluctuations in the local velocity of sound $`c^2(r)`$, depends on the variance parameter

$$\nu (\lambda )\frac{c^4(r)_\lambda }{c^2(r)_\lambda ^2}1\nu (a)\left(\frac{a}{\lambda }\right)^3,$$

where $`\lambda =2\pi /q`$ is the phonon wavelength, and $`a`$ is the scale at which elementary fluctuations occur (i.e. for QCs $`aD_{cl}`$). Let us have $`\nu (a)1`$. Since $`c^2(r)`$ is always positive, the only way this can occur is by having a small number of ”hard” regions for which $`c^2`$ is larger than the average, which dominate the variance, and a much larger number of ”soft” regions. If the ”hard” scatterers (of size $`D_{cl}`$) are isolated, the only propagating modes are those of the ”soft” background medium. The scatterers act as rigid inclusions in the medium. Roughly, the ”hard” scatterers simply increase the effective elastic constant by a factor proportional to the small volume factor they occupy. The above argument neglects the local modes centred around the ”hard” scatterers. For a single scatterer they would be localized and have a high frequency. When they are dilute and uncorrelated, so that they couple weakly, they can only form an relatively high-frequency optical band. On the other hand, when they are correlated and coupled sufficiently strongly, they can dominate the elastic properties and the low-frequency velocity and damping of sound. As a rule of thumb we can estimate the characteristic frequency for mode hybridization as $`c_\alpha /D_{cl}`$. In this region phonon wavefunctions are repetitively localized on the clusters and this recurrent localization comes from the fact that, unlike for periodic crystals, it is not possible for the wavelength to be commensurate simultaneously with all inter-cluster distances in a quasiperiodic structure. Evidently this cluster vibration mode is not an exact eigenstate. It interacts with other vibration modes of similar energy and as well with acoustic phonons. This interaction affects both the cluster vibration mode and the phonons, which are for the same reason also not exact eigenstates. In other words due to the above described mode - hybridization the excitations will be broadened and shifted.

Physically these cluster vibrations are caused by a local deviation of the force constant matrix and atomic mass from the average values. The hybridization phonon broadening $`\mathrm{\Gamma }`$ for a phonon with wave vector $`𝐤`$, polarization $`j`$, and frequency $`\omega _0`$ depends on a ”concentration” (i.e. density of states $`g(𝐤)`$) of these cluster vibrations and is proportional to the phonon - cluster mode scattering matrix $`\widehat{t}`$

$`\mathrm{\Gamma }(\omega _0(𝐤,𝐣))=𝐠(𝐤){\displaystyle \frac{\mathrm{𝟏}}{\mathrm{𝟐}}}{\displaystyle \frac{\mathrm{}𝐤,𝐣|\widehat{𝐭}𝐤,𝐣}{\omega _\mathrm{𝟎}(𝐤,𝐣)}}.`$ (8)
To obtain total hybridization broadening this expression (8) has to be averaged and integrated over all cluster vibrations with frequencies approximately equal to $`\omega _0`$. If the structure of the mode does not strongly depend on its frequency, and their distribution is smooth on a scale of their width, $`\mathrm{\Gamma }`$ will have $`k`$-dependence coming mainly from the density of states factor in (8). Using the arguments borrowed from the standard glass theory PH80  we can conclude that $`gk^4`$.

## IV Discussion and Conclusion

Let us summarize now the experimental results and the theoretical interpretation presented in this paper. The physical essence of the model is as follows. If the wavelength $`\lambda `$ of the sound is larger than the characteristic cluster size $`D_{cl}`$ we can assume that each cluster is subject to a uniformly distributed stress. However due to not spherical cluster shape and boundary conditions at their surfaces, the resulting deformation is not uniform. It varies considerably over the dimension of a cluster (not over sound wavelength as in a uniform bulk body). Hence sound broadening due to thermal conduction (Akhiezer mechanism) is essential for the case. To be specific this scenario can be rationalized as sound modes (mainly longitudinal but as we have seen also transverse) somehow perturb the manifold of optic modes or QC cluster vibrations (the characteristic features of QC materials taken into account by the model). These perturbations in terms of Gruneisen parameters are reduced to temperature variations, and the latter ones lead to thermo-diffusional relaxational sound absorption. It might at first sight seem that the model contains no QC-specific features: but in fact all QC properties are hidden in the material parameter values entering the formula.

The discussed above (in the previous section III) second broadening mechanism \- resonance hybridization of sound and cluster vibration modes - can compete with the Akhiezer absorption even for the longitudinal modes in the relatively high $`q`$-region. All the more it is true for the transverse waves where the Akhiezer broadening is expected to be less efficient. Fortunately they do have different $`q`$-dependencies that allow us to disentangle them analysing experimental data. To span a wide range of possibilities let us discuss first the Akhiezer mechanism. To compare the expressions with neutron data it is more convenient to use:

(i) the absorption coefficient $`\mathrm{\Gamma }[s^1]=\alpha [cm^1]c_\alpha `$;

(ii) the wave vector $`q`$ instead of $`\omega `$.

Thus we come from (5) to

$`\mathrm{\Gamma }={\displaystyle \frac{\kappa \gamma _{av}^2T}{\rho c_\alpha ^3}}q^2.`$ (9)
The proposed model can be checked against experimental data along three lines: the wave vector dependence of the acoustic mode broadening which should be proportional to $`q^2`$, its temperature variation and its order of magnitude.

The $`q^2`$ increase of the acoustic phonon width was generally observed for longitudinal acoustic excitations. For $`TA`$ modes the width increase seems to be more abrupt, (for a wave vector larger than $`0.3\AA ^1`$) and goes rather as a $`q^4`$ law as shown in Figs. 2 and 3. Presented by the solid line in Fig. 1 a $`q^2`$ fit to the observed widths, illustrates this statement, and besides, can be used to extract some quantitative information on the magnitudes of $`q^2`$ and $`q^4`$ parameters. As expected, the coefficient of the fit is twice as large in the $`iAlPdMn`$ phase as in the $`iZnMgY`$ one (9.8 and 4.9 $`meV/\AA ^2`$). In the $`iZnMgY`$, we also found that the $`LA`$ mode broadens twice as fast as the $`TA`$ modes. More accurate inspection of the data presented in Fig. 1 clearly shows that for a region close to the mixed regime (i.e. to $`q0.6\AA `$) the broadening is more rapid than a $`q^2`$ law. It can be attributed to Rayleigh scattering arising from local fluctuation in sound velocity due to either mass density or elastic constant fluctuations (in own turn related to the cluster structure of all QCs) or to acoustic - optic mode hybridization. In mathematical form both phenomena lead to $`q^4`$ broadening PH80 , though of course the Rayleigh scattering seems generally too weak in homogeneous materials like QCs.

The next test concerns temperature dependences. Since at high enough temperatures $`\kappa 1/T`$, in the present approximation the effect of the temperature dependent factors cancels, and therefore the absorption due to Akhiezer mechanism can only weakly depend on temperature. It is worth noting also that the very possibility to characterize the system by only one Gruneisen function is based on the assumption that the dependence of the energy levels on the volume (or more generally on the deformations $`u_{ik}`$) is expressible in terms of a single characteristic energy. This assumption is correct for Einstein or Debye models, partly also for conventional (with relatively small elementary cell) crystalline solids but not evident at all for QC systems where a number of different contributions to the free energy can control the thermodynamic properties (see discussion in SF02 , SL02 ).

Thus in this approximation (namely, in the high temperature regime where $`T>\mathrm{\Theta }_D`$, $`\mathrm{\Theta }_D`$ being the Debye temperature, 400 - 500 K, within the classical Debye approach valid in this region, $`\kappa 1/T`$ (all other parameters determining $`\mathrm{\Gamma }`$ do not depend noticeably on $`T`$) and $`\mathrm{\Gamma }`$ is temperature independent in agreement with experimental data. Of course it is only an approximation and we are aware that QCs are not classical Debye insulators, and besides we are not in the regime $`T\mathrm{\Theta }_D`$, but it identifies correctly the characteristic scales in the problem. A detailed temperature dependence of the lattice dynamics has only been carried out in the $`iAlPdMn`$ phase. At $`T=1050K`$ the slope of the acoustic transverse acoustic mode displays only a $`10\%`$ decrease as compared to room temperature and the broadening of the modes did not show any significant variation. This is thus in agreement with the model since the Debye temperature of the $`iAlPdMn`$ phase is about $`500K`$(see e.g. SF02 ).

Quantitative comparison of our model predictions with experimental data is more difficult since there are only scarce data available for the model input parameters and their temperature dependences (there are no systematic measurements of all needed material parameters, and experimental data are still not very accurate). Thus from here on in this section we shall not attempt to maintain numerical accuracy, but only indicate the form of the answer. Our model can be used to estimate the $`q^2`$ coefficient in the phonon line broadening. Namely, from SF02 , SL02 , GS00 :

$$\kappa 1\frac{W}{mK}=10^5\frac{erg}{scmK},$$

$$\rho =5g/cm^3;\gamma _{av}1,$$

and, besides, $`T300K`$. Using also the literature (BB93 , BB95 ) data for i-QC materials ($`ZnMgY`$ $`c_l=4.810^5cm/s`$, $`c_t=3.110^5cm/s`$), and neutron measurements (BB93 , BB95  and our data shown in Figs. 1 - 3), one can find that at $`q0.5\AA ^1`$, for the longitudinal phonons, $`\mathrm{\Gamma }_l1.5meV`$, and for the transverse modes, depending on propagation directions $`\mathrm{\Gamma }_t1meV`$ ; for $`AlPdMn`$ ($`c_l=6.310^5cm/s`$, $`c_t=3.510^5cm/s`$), at the same $`q0.5\AA ^1`$, $`\mathrm{\Gamma }_t2meV`$ (no data for longitudinal mode line-widths). Putting all values together we find for the $`q^2`$ coefficient about $`10meV/\AA ^2`$ in reasonable agreement with the experimental value quoted above.

One more interesting line of thought is to apply our results to estimate the anisotropic Gruneisen parameters, introduced in (1). The observed difference in width increase rate between transverse and longitudinal excitations means that a different Gruneisen parameter should be used in each case. Comparing experimental data for longitudinal and transverse modes in the same material (for the moment such data are available only for $`iZnMgY`$) we can conclude that the volume Gruneisen parameter entering the longitudinal phonon broadening (5) should be four times larger than the shear anisotropic Gruneisen coefficient which determines the transverse phonon line broadening (6).

These Gruneisen parameters can be seen as a phenomenological way of taking into account the interaction between $`LA`$ or $`TA`$ modes and optical branches. Various phonon interaction processes result when anharmonic terms of the third (and higher) order in the displacements are taken into account. The first anharmonic term corresponds to the decay of one phonon into two or to the coalescence of two colliding phonons into one. For conventional crystals, usually the main contribution comes from processes within the same optical branch. For QCs, the dispersionless character of the optical branches could lead to a situation where the conditions for phonon decay or recombination are satisfied above a finite threshold wave vector (corresponding to the crossing with the lowest frequency optical branch), and not for a discrete set of wave vectors but for a whole spherical shell in $`q`$ space.

The coefficient at $`q^4`$ for the resonance hybridization broadening, is a model dependent quantity. However, it can be always presented in the following form PH80

$`\alpha _{\alpha ,\mathrm{res}}=\mathrm{\Lambda }_\alpha {\displaystyle \frac{\omega }{c_\alpha }}\left({\displaystyle \frac{\omega }{\omega _{cl}}}\right)^3,`$ (10)
where $`\mathrm{\Lambda }_\alpha `$ is a model and mode polarization dependent coefficient, and $`\omega _{cl}`$ is a characteristic frequency for cluster vibrations. To illustrate this issue we show in Figs. 2 and 3 $`q`$-dependences of line width for longitudinal and transversal modes in the $`iZnMgY`$ and $`iAlPdMn`$ QCs. These results are clearly indicating that for the longitudinal modes the broadening are governed mainly by the Akhiezer mechanism, whereas for the transversal waves $`q^4`$ fitting leads to a reasonable agreement with the data. Moreover the coefficient at $`q^4`$ found from such a fitting is conformed with (10) describing resonance hybridization sound absorption.

Of course the imperfect knowledge of the parameters in a large temperature interval makes our predictions only qualitatively or semi-quantitatively correct, and at this stage, a number of open questions must be stressed. For example no forbidden gaps have been observed experimentally. There is also some inconsistency between thermodynamic and inelastic neutron scattering data SF02 , SL02 . A possible origin of this inconsistency may be related to contributions, say to the specific heat, from the cluster vibrations. It is worth noting, however, that all scattering experiments measure a dynamic structure factor $`S(q,\omega )`$, which is the Fourier transform of the displacement correlation function, and therefore does not carry direct information about propagation or non-propagation of modes. But to put these speculations on a firm footing, further experimental and theoretical efforts are required. Nevertheless for a model with such a small amount of physical input, our results show quite good agreement with experiments (the order of magnitudes together with its evolution with $`T`$ and $`q`$). In addition we can give some qualitative predictions concerning Gruneisen parameters and anharmonicity in different QC materials. It is worth noting in this respect one very recent theoretical prediction ZG02  that Gruneisen parameters should diverge close to a quantum critical point. In a certain sense QC phonon and electron states are critical over the whole region of the QC state stability. However, it should be noted that dynamics of QC is still a developing field and much of the excitement arises from the possibility of discovering novel physics beyond say the classical paradigms discussed here.

As this paper was being written for publication we became aware of parallel efforts CF03 , RF03  to investigate the crossover from propagating to strongly attenuated acoustic modes in densified silica glasses. Although physically the two systems (QCs and glasses) are very different, acoustic mode broadening reported in these papers and its interpretation (Akhiezer attenuation due to optical mode perturbations and acoustic - optic modes scattering and hybridization) are quite similar to our results. Of course the nature of these optical modes is different in each case: in glasses it is related to disorder (in silica glasses it corresponds to librations of $`SiO_4`$ tetrahedra), in QCs the optic modes are related to cluster vibrations or, in other words, to the translational or orientational frustrations intrinsic to all QCs.

###### Acknowledgements.

One of us (E.K.) acknowledges support from INTAS (under No. 01-0105) Grants. We thank T. Janssen for thought-provoking discussions.

Figure caption

Fig. 1

Dispersion relation measured around the strong 2-fold Bragg reflection with $`N/M`$ indices equal to 52/84 and propagating along a 2-fold axis in the $`iAlPdMn`$ (the upper figure) and $`iZnMgY`$ phase (the lower figure). Results are presented in an extended zone scheme, the pseudo Brillouin zone boundaries are shown as vertical dashed lines. The transverse acoustic mode positions are shown as full circles and their width as open one. The dashed line is the linear dispersion relation as deduced from ultrasonic measurements and the solid line is a $`q^2`$ fit to the width increase. The other open symbols correspond to dispersionless optic like excitations, whose width is of the order $`4meV`$.

Fig. 2

Line width for longitudinal (the upper figure) modes propagating along a 5-fold axis (experimental data and $`q^2`$-fitting) and for the transversal modes (the lower figure) propagating along a 2-fold axis (experimental data and $`q^4`$-fitting) in the $`iZnMgY`$ phase.

Fig. 3

Line width for the transversal mode propagating along a 2-fold axis (experimental data and $`q^4`$-fitting) in the $`iAlPdMn`$ phase.


format: text

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# Second-order transverse magnetic anisotropy induced by disorders in the single-molecule magnet Mn12

## I Introduction

Single-molecule magnets (SMMs) are three-dimensional arrays of identical molecules. Each molecule has a large effective spin with a large magnetic anisotropy barrier, and responds to an external magnetic field as a nanoscale, single-domain magnetic particle. As such SMMs are ideal for high-density magnetic storage devices. The most extensively studied SMM is \[Mn12O12(CH3COO)16(H2O)4\] $``$2(CH3COOH)$``$4(H2O) (hereafter Mn12).LIS80  A single molecule of Mn12 (Fig. 1) has an effective ground-state spin of $`S=10`$ with a magnetic easy axis along the crystal $`c`$ axis (i.e., $`z`$ axis), and has S4 symmetry. Low-temperature magnetization hysteresis loop measurements on Mn12 revealed steps at quantized magnetic fields, in which macroscopic quantum tunneling (MQT) occurred between spin-up states and spin-down states through the magnetic anisotropy barrier.SESS93 ; FRIE96  Many competing models have been proposed to understand various features of the MQT: fourth-order transverse anisotropy,VILL94  thermally assisted quantum tunneling,FRIE96 ; GARA97  the Landau-Zener effect,RAED97  and dipolar interactions with dynamic hyperfine fields.PROK98  However, the observation of quantized steps that are forbidden by the symmetry of a single Mn12 molecule remains a long-standing puzzle. It is imperative to fully understand the MQT because higher tunneling rates imply the loss of magnetically stored information, while tunneling is useful in quantum superposition of states crucial to quantum computingLEUE01-NAT .

A general effective single-spin Hamiltonian for SMMs is, to fourth order,

$`=DS_z^2+E(S_x^2S_y^2)+C_1S_z^4+C_2(S_+^4+S_{}^4)+^{}+g\mu _B\stackrel{}{B}\stackrel{}{S},`$ (1)
where $`D`$ is the uniaxial anisotropy parameter, $`E`$ is the second-order transverse anisotropy parameter, $`S_z`$ is a spin operator projected onto the easy axis, $`C_1`$ and $`C_2`$ are the fourfold longitudinal and transverse anisotropy parameters, $`^{}`$ contains all possible fourth-order terms that break S4 symmetry, and the last term is the Zeeman interaction. The experimental parameter values are $`D=0.55`$ K, $`C_1=0.00117`$ K, and $`C_2=\pm `$2.88$`\times `$10-5 K.BARR97  The MQT is ascribed to the transverse terms in Eq. (1). According to the S4 symmetry of a Mn12 molecule, $`E=0`$ and $`^{}=0`$ so that the MQT is caused by $`C_2`$ alone and is allowed between states whose eigenvalues of $`S_z`$ differ by integer multiples of 4. However MQT is observed between states that violate this rule. To understand these unexplained tunneling steps, it is necessary to include a lower symmetry than S4. Transverse fields caused by internal fields (exchange, dipolar, and hyperfine fields) or field misalignment could induce these steps, but resulting tunneling rates will be too small compared to measured valuesMERT01 . Thus, a nonzero $`E`$ value is needed to expedite tunneling assuming that $`^{}`$ is negligible. So far, two different theories have been proposed in this regard. Chudnovksy and GaraninCHUD01  proposed that possible dislocations in single crystals may provide a broad continuous distribution of $`E`$ and showed that a broad continuous range of $`E`$ values is required to explain experiments. Detailed x-ray diffraction studies by Cornia et al.CORN02  suggested that disorder caused by acetic-acid (referred to as HAc) solvent molecules may break the S4 symmetry and induce substantial locally varying $`E`$ values. As discussed in Sec. IIA, such disorder is expected on general grounds. Recently, two completely different experimentsBARC02 ; HILL03  have been performed to elucidate the sources of a low symmetry in Mn12. Magnetic quantum tunneling measurementsBARC02  showed that tunneling splittings (between states whose eigenvalues of $`S_z`$ do not differ by integer multiples of 4) have much narrower distributions than what the dislocation-induced theory suggested. They also showed that the largest $`E`$ value for low symmetry molecules is 0.01 K, which is twice larger than what Cornia et al.CORN02  calculated. Electron paramagnetic resonance measurements showed that an upper bound on the $`E`$ values is 0.014 K,HILL03  and that some molecules may have an appreciable easy-axis tilt away from the crystal $`c`$ axis.HILL03-2

The two different experiments revealed consistent results that may not be fully explained by either of the two proposed theories. Thus, there is a need for a new theory or a more refined theory that is consistent with the experimental results. In this regard, we investigate the sources of a low symmetry in Mn12 within density-functional theory (DFT). Specifically, we consider both positional disorder due to the HAc solvent molecules and orientational disorder caused by methyl-group rotations in Mn12 molecules. We find that hydrogen bonding between the Mn12 molecules and the solvent molecules is crucial in the second-order transverse anisotropy. We calculate the magnetic anisotropy parameters and the easy-axis tilting angles from the crystal $`c`$ axis for representative configurations induced by the positional disorder that will be described later. We find that the $`E`$ value increases upon geometry relaxation, and that there exist relationships, due to symmetry, between the $`E`$ values for the representative configurations. We also calculate torsional barriers and the magnetic anisotropy parameters for configurations induced by the orientational disorder. Our calculated $`E`$ values are comparable to the experimental data, while the easy-axis tilting angles remain small. In Sec. II, we describe our method and model for the positional disorder and for the orientational disorder. In Sec. III, we show our results and discuss their consequences. In Sec. IV, we present our conclusion.

## II Method and Model

In our DFT calculationsKOHN65 , we use spin-polarized all-electron Gaussian-orbital-based Naval Research Laboratory Molecular Orbital Library (NRLMOL) PEDE90  within the Perdew-Burke-Ernzerhof (PBE) generalized-gradient approximation (GGA) for the exchange-correlation potential.PERD96  We consider the following simplified form of Mn12: \[Mn12O12(CH3COO)8(HCOO)8(H2O)4\] $``$ 2(CH3COOH) where 8 formates (HCOO) substituted for 8 acetates (CH3COO, referred to as Ac) bridging Mn4+ ions in the inner cubane and Mn3+ ions in the outer crown (Fig. 1). For simplicity, we do not include the water molecules of crystallization. Instead of a periodic structure, we examine an isolated Mn12 molecule surrounded by four HAc solvent molecules. The zero-field magnetic anisotropy barrier for the $`S=10`$ ground-state manifold does not change much with our simplification nor with attachment of the solvent molecules. The total magnetic moment for the ground state was confirmed to be $`20\mu _\mathrm{B}`$, which is in good agreement with experiment. It is common that the x-ray deduced experimental geometry has underestimated C-H and O-H bond lengths in comparison to standard hydrogen bond lengths, which results in large self-consistent forces on hydrogen atoms as large as an order of 1 hartree/bohr.PARK03-Mn4  Therefore, we use as an initial geometry the experimental geometry with hydrogen positions corrected such that all C-H (O-H) bond lengths become 1.1 Å (0.96 Å). Then the initial geometry is self-consistently relaxed using NRLMOL until forces exerted on all atoms are small.

### II.1 Positional disorder

A single Mn12 molecule has four HAc solvent molecules, each of which is shared by two neighboring Mn12 molecules. From the perspective of the HAc molecule, there are two equivalent ways to place one HAc molecule between two Mn12 molecules. That is, the methyl group (CH3) in HAc can point toward a Mn12 molecule or away from it (Fig. 2). In the latter case, there is hydrogen bonding between the oxygen atom O(2) in the Mn12 molecule and the oxygen atom O(1) in the solvent molecule (Fig. 1). We refer to this configuration as head and the other as tail (Fig. 2). There are a total number of 16 ways to place four HAc molecules around a Mn12 molecule. Only six of them are inequivalent by symmetry as illustrated in Fig. 2 where $`n`$ denotes the number of the head configurations. The populations of the six configurations are shown in Table 1. The configurations $`n=1`$, $`n=2`$ trans, $`n=2`$ cis, and $`n=3`$ break the S4 symmetry, while $`n=0`$ and $`n=4`$ preserve the S4 symmetry. The three configurations, $`n=1`$, $`n=2`$ cis, and $`n=3`$, can cause easy-axis tilts from the crystal $`c`$ axis which coincides with the $`z`$ axis, the easy axis without considering the positional disorder.

To examine if the head configuration affects the magnetic anisotropy in the same way as the tail, we consider the following three configurations: (i) two tails only in a twofold symmetric way (trans), (ii) three heads and one tail, and (iii) three heads only. We calculate the $`D`$ and $`E`$ values for an initial geometry of each configuration. We find that configuration (i) provides $`D=0.56`$ K and $`E=0.00053`$ K and that configurations (ii) and (iii) provide the same parameter values of $`D=0.58`$ K and $`E=0.0035`$ K. These results imply that the tail configuration does not substantially contribute to the second-order transverse anisotropy. It is thus sufficient to carry out DFT calculations on head-only configurations, which reduces significantly the computation time. Hereafter, unless specified, when we refer to the $`n=1`$ configuration, it indicates only one head HAc added to a Mn12 molecule without three tail HAc molecules (see the leftmost figure in Fig. 3). The same rule is applied to the rest of the configurations. We also find that both the transverse magnetic anisotropy and the easy-axis tilting angle increase by a factor of 3 upon geometry relaxation.

Especially since we relax an isolated Mn12 molecule with solvent instead of a periodic structure, it is worthwhile to check if DFT provides a correct hydrogen bond between two isolated atoms using a simple example system. For this purpose, we carry out DFT calculations for a water dimer. Using its fully relaxed geometry, we obtain the distance between the two oxygen atoms, the O-H-O angle, and its binding energy. They are in excellent agreement with experimental dataODUT80 ; CURT79 ; BENT80  as shown in Table 2. This result confirms that DFT captures the hydrogen bonding between Mn12 molecules and solvent molecules, and that relaxation of the initial geometries should provide physically refined geometries.

With a well relaxed geometry a second-order single-spin Hamiltonian is calculated considering spin-orbit coupling only.PEDE99  The Hamiltonian has a form of $`_{\mu ,\nu =x,y,z}\gamma _{\mu \nu }S_\mu S_\nu `$. Here $`\gamma _{\mu \nu }`$ is obtained from the calculated occupied and unoccupied states of the well relaxed geometry and contains the information on the second-order magnetic anisotropy parameters and the principal axes of the magnetic anisotropy. By exploiting symmetry arguments appropriate to the Mn12 and the solvent molecules, we can explore all of the six different configurations (Fig. 2) using only the following two configurations. Once the single-spin Hamiltonians for the $`n=0`$ and $`n=1`$ configurations are calculated, those for the remaining four configurations can be obtained by rotations of coordinates. For instance, we can describe the Hamiltonian for $`n=2`$ trans (cis), $`[n=2]`$, in terms of those for $`n=0`$, $`[n=0]`$, and $`n=1`$, $`[n=1]`$, using a rotation matrix $`R`$ (see Fig. 3).

$`[n=0]`$ $``$ $`{\displaystyle \underset{\mu ,\nu =x,y,z}{}}\gamma _{\mu \nu }^{(0)}S_\mu S_\nu ,[n=1]{\displaystyle \underset{\mu ,\nu =x,y,z}{}}\gamma _{\mu \nu }^{(1)}S_\mu S_\nu ,`$ (2)
$`[n=2]`$ $`=`$ $`{\displaystyle \underset{\mu ,\nu =x,y,z}{}}\gamma _{\mu \nu }^{(1)}[S_\mu S_\nu +R(S_\mu )R(S_\nu )]{\displaystyle \underset{\mu ,\nu =x,y,z}{}}\gamma _{\mu \nu }^{(0)}S_\mu S_\nu `$ (3)
$``$ $`{\displaystyle \underset{\mu ,\nu =x,y,z}{}}\gamma _{\mu \nu }^{(2t),(2c)}S_\mu S_\nu `$
$`\gamma _{xy}^{(2t)}`$ $`=`$ $`2\gamma _{xy}^{(1)},\gamma _{xz}^{(2t)}=0,\gamma _{yz}^{(2t)}=0,`$ (4)
$`\gamma _{xy}^{(2c)}`$ $`=`$ $`0,\gamma _{xz}^{(2c)}=\gamma _{xz}^{(1)}\gamma _{yz}^{(1)},\gamma _{yz}^{(2c)}=\gamma _{xz}^{(1)}+\gamma _{yz}^{(1)}`$ (5)
$`\gamma _{xy}^{(3)}`$ $`=`$ $`\gamma _{xy}^{(1)},\gamma _{xz}^{(3)}=\gamma _{yz}^{(1)},\gamma _{yz}^{(3)}=\gamma _{xz}^{(1)}`$ (6)
where $`\gamma ^{(2t)}`$, $`\gamma ^{(2c)}`$, and $`\gamma ^{(3)}`$ stand for the $`\gamma `$ matrices for the $`n=2`$ trans, $`n=2`$ cis, and $`n=3`$ configurations, respectively. Here we show only the off-diagonal elements of the $`\gamma `$ matrices. Since $`n=0`$ has the S4 symmetry, $`\gamma _{xy}^{(0)}`$=$`\gamma _{xz}^{(0)}`$=$`\gamma _{yz}^{(0)}`$=0. We have also verified this numerically.

### II.2 Orientational disorder

The methyl group in Ac can rotate about the C-C single bond. During the rotation, the energy of the methyl group will change. The difference between the maximum and the minimum energy is called a torsional barrier. For an isolated Ac molecule, the torsional barrier is calculated to be about 320 K, which is comparable to the thermal energy at room temperature. So it is interesting to examine if the orientational disorder caused by rotations of the methyl groups can induce the appreciable second-order transverse anisotropy. We consider rotations of the methyl groups in a Mn12 molecule, and there are three inequivalent Ac sites. The methyl groups in the Ac molecules bridging the inner Mn ions and the outer Mn ions will have less freedom to rotate and therefore a smaller effect on the transverse anisotropy. The methyl groups of type A (Fig. 1) are close to the HAc solvent molecules so they also have less freedom to rotate. Thus we rotate the methyl groups of type B (in the Ac molecules that are free from the HAc molecules) with the methyl groups of type A fixed. In this study, we do not allow solvent-induced symmetry breaking and do not consider geometry relaxation induced by methyl rotations. We consider an initial geometry of the $`n=4`$ configuration with several methyl groups of type B rotated, and calculate the torsional barriers and the magnetic anisotropy parameters.

## III Results

### III.1 Positional disorder

The well relaxed geometry for the $`n=0`$ configuration gives rise to $`D=0.54`$ K and $`E=0`$. The well relaxed geometry for the $`n=1`$ configuration provides $`D=0.54`$ K, $`E=0.008`$ K, and the easy-axis tilting angle $`\theta =0.4^{}`$. Using this result and Eqs. (2)-(6), we calculate $`D`$, $`E`$, and $`\theta `$ for the $`n=2`$ trans, $`n=2`$ cis, $`n=3`$, and $`n=4`$ configurations (Table 1). The $`D`$ value does not vary much among the different configurations. (Note that $`D=0.55`$ K without solvent molecules.PEDE99 ) The $`E`$ value for $`n=1`$ is the same as that for $`n=3`$ and is one half of that for $`n=2`$ trans. The $`E`$ value for $`n=2`$ cis is two orders of magnitude smaller that that for $`n=1`$. The largest $`E`$ value arises from $`n=2`$ trans, while the largest $`\theta `$ comes from $`n=2`$ cis. The $`E`$ values for the low-symmetry configurations are determined by all the off-diagonal elements of the $`\gamma ^{(1)}`$ matrix, while the easy-axis tilts are due only to the nonzero $`\gamma _{xz}^{(1)}`$ and $`\gamma _{yz}^{(1)}`$ values \[Eqs. (2)-(6)\]. For the positional disorder, the magnitudes of all the off-diagonal elements of the $`\gamma ^{(1)}`$ matrix are very small compared to those of the diagonal elements. Therefore, there is no appreciable easy-axis tilt and there is a relation between the $`E`$ values for different configurations. The $`n=2`$ cis configuration does not have a significant contribution to the transverse anisotropy. If the magnitudes of the off-diagonal elements are significant, there is a substantial easy-axis tilt and the $`E`$ values for the distinctive configurations are not correlated. Additionally, the $`E`$ value for $`n=2`$ cis has the same order of magnitude as those for the other low-symmetry configurations. This occurs when extra electrons are donated to a Mn12 molecule since the locations of the extra electrons are intrinsically dependent on donor locations.PARK03-prep  In comparison to Cornia et al.’s results,CORN02  our calculated $`E`$ values are larger by a factor of 3 and our easy-axis tilting angle is almost the same. In comparison to the experimental data,BARC02 ; HILL03 ; HILL03-2  our largest $`E`$ value is in good agreement but our largest easy-axis tilting angle is smaller than 1.

To examine the effect of the positional disorder on the local magnetic anisotropy, we calculate the single-ion anisotropy parametersBARU02  and the local magnetic easy-axis tilts for the three inequivalent Mn sites in two different environments. These three sites are the cubane Mn4+ ion (at site c in Fig. 1) and two Mn3+ ions (at sites r and b in Fig. 1). The two environments correspond to (i) the head and (ii) tail configurations. For the environments (i) and (ii) we use a well relaxed $`n=2`$ trans (two heads and two tails) geometry. Before showing our results, we describe our method. The lowest-order energy shift $`\mathrm{\Delta }_2`$ due to spin-orbit coupling $`V_{LS}`$ isPEDE99

$`\mathrm{\Delta }_2`$ $`=`$ $`{\displaystyle \underset{\sigma ,\sigma ^{}}{}}{\displaystyle \underset{ij}{}}{\displaystyle \frac{\psi _{i\sigma }|V_{LS}|\psi _{j\sigma ^{}}\psi _{j\sigma ^{}}|V_{LS}|\psi _{i\sigma }}{ϵ_{i\sigma }ϵ_{j\sigma ^{}}}},`$ (7)
where $`ϵ_{i\sigma }`$ ($`ϵ_{j\sigma ^{}}`$) denotes the energy of the $`i`$th occupied ($`j`$th unoccupied) unperturbed state whose wavefunction is $`|\psi _{i\sigma }`$ ($`|\psi _{j\sigma ^{}}`$). The first sum runs over spin-up and spin-down states and the second sum over all occupied and unoccupied states. A wavefunction of the system is expanded in a sum of contributions associated with each atom, $`|\psi _{i\sigma }`$$`=`$$`_\alpha |\psi _{i\sigma }^\alpha `$ and $`|\psi _{j\sigma ^{}}`$$`=`$ $`_\alpha |\psi _{j\sigma ^{}}^\alpha `$, where the sums run over all atoms. Thus, $`\mathrm{\Delta }_2`$ can be written in terms of projected terms onto each atom and mixed terms between different atoms as follows:

$`\mathrm{\Delta }_2`$ $`=`$ $`{\displaystyle \underset{\alpha }{}}{\displaystyle \underset{\sigma ,\sigma ^{}}{}}{\displaystyle \underset{ij}{}}{\displaystyle \frac{\psi _{i\sigma }^\alpha |V_{LS}|\psi _{j\sigma ^{}}^\alpha \psi _{j\sigma ^{}}^\alpha |V_{LS}|\psi _{i\sigma }^\alpha }{ϵ_{i\sigma }ϵ_{j\sigma ^{}}}}+{\displaystyle \underset{\alpha \beta \gamma \delta }{}}{\displaystyle \underset{\sigma ,\sigma ^{}}{}}{\displaystyle \underset{ij}{}}{\displaystyle \frac{\psi _{i\sigma }^\alpha |V_{LS}|\psi _{j\sigma ^{}}^\beta \psi _{j\sigma ^{}}^\gamma |V_{LS}|\psi _{i\sigma }^\delta }{ϵ_{i\sigma }ϵ_{j\sigma ^{}}}}`$ (8)
where the first sum of the mixed term runs over all cases where at least two of the indices $`\alpha \beta \gamma \delta `$ are different. Based on the assumption that the contributions associated with each atom, $`|\psi _{i\sigma }^\alpha `$, have small interatomic overlap, which is the case for Mn12, the mixed terms are expected to be negligible. This is true considering the relative magnitude of the Coulomb potential near an atom compared to the interstitial region. Thus $`\mathrm{\Delta }_2`$ is approximately equal to the tensor sum of the projected terms onto all atoms, the first term in Eq. (8). Regardless of the types of the environments, a cubane Mn4+ ion has the local easy axis almost in the $`xy`$ plane (the local $`E`$ value is of the same order as the local $`D`$ value) and the two crown Mn3+ ions have the local easy axis close to the $`z`$ axis. Therefore the Mn3+ ions contribute most of the total magnetic anisotropy. Since the Mn4+ ions are far away from the solvent molecules, the local $`E`$ value for the head configuration is the same as that for the tail. For the two inequivalent Mn3+ ions, the local $`E`$ value is sensitive to the environments, while the local $`D`$ value and the local easy-axis tilting angles are not sensitive to them. Especially for the Mn3+ ions of type b, the local $`E`$ value for the tail configuration is an order of magnitude smaller than that for the head. This large difference in the local $`E`$ values of the head and tail configurations leads to the large global $`E`$ value.

We also calculate tunnel splitting $`\mathrm{\Delta }_{10,4}`$ between $`M_s=10`$ and $`M_s=4`$, where $`M_s`$ is an eigenvalue of $`S_z`$ (Table I) for the six distinctive configurations perturbatively and by exact diagonalization. We use our calculated values for $`D`$ and $`E`$ and the experimental valuesBARR97  for $`C_1`$ and $`C_2`$. The tunneling between $`M_s=10`$ and $`M_s=4`$ is allowed due to the nonzero second-order transverse anisotropy but the magnitude of the tunnel splitting is mostly governed by the fourth-order transverse anisotropy. So the tunnel splitting is very dependent on the $`C_2`$ value but less on the $`E`$ value. As shown in Table I, if we reduce the $`C_2`$ value by one half from the experimental value while keeping other parameter values constant, the tunnel splitting is reduced by an order of magnitude. Thus, the experimental value of $`\mathrm{\Delta }_{10,4}`$\[MERT01, \] may not be a good indicator of the magnitude of the $`E`$ value.

### III.2 Orientational disorder

When the four methyl groups of type B are rotated relative to those of type A in the $`n=4`$ configuration, we find that there are at least four local energy minima at the rotation angles of $`10^{}`$, $`25^{}`$, 0, and 30 where $`0^{}`$ denotes the experimental geometry. Since the four methyl groups are rotated simultaneously, we have to divide by 4 to obtain the torsional barriers per methyl group for each rotation angle. As shown in Table 4, the torsional barriers at the three nonzero rotation angles are comparable to the thermal energy at room temperature. So we consider the three twofold symmetric configurations, which correspond to $`n=4`$ with two methyl groups of type B across from each other rotated by $`10^{}`$, $`25^{}`$, and 30. Our calculations show that the $`E`$ values for all three angles are on the order of 10-4 K, which is much smaller than those due to the positional disorder (Table 4).

## IV Conclusion

Considering the solvent positional disorder and the orientational disorder of the methyl groups in the Mn12 molecules, we investigated, within density-functional theory, the sources of the second-order transverse magnetic anisotropy in Mn12. We found that only hydrogen-bonded solvent molecules contribute to the symmetry-breaking transverse anisotropy, and that geometry relaxation is necessary from the standpoint of quantitative prediction. For the positional disorder, the large $`E`$ value is due to the large difference between the local $`E`$ values of the two different environments (the head and tail configurations). There are no significant easy-axis tilts from the $`z`$ axis for the low-symmetry configurations. Accordingly, the $`E`$ values for the different configurations are correlated. The orientational disorder contributes to the $`E`$ value much less than the positional disorder. Our largest calculated $`E`$ value from the positional disorder quantitatively agrees with the experimental data. However unresolved issues remain. That is, the experimental $`E`$ values suggest a continuous distribution rather than a discrete distribution that is predicted by the positional disorder.

## Acknowledgments

This work was supported in part by the ONR (Grant No. N000140211045), the NRL, the DoD HPCMPO and CHSSI program, and the W.M. Keck Foundation (K.P.).


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# Reply to the comment on ^''Quantum nonlocality for a three-particle nonmaximally entangled state without inequaltiy^''

## Abstract

This is to reply to Cereceda’s comment on $`^{^{\prime \prime }}`$Quantum nonlocality for a three-particle nonmaximally entangled state without inequaltiy$`^{^{\prime \prime }}`$

In a recent paper , I show that the following three-particle nonmaximally entangled state can exhibit quantum nonlocality without inequaltiy

$$|\psi _{1,2,3}=\mathrm{cos}\theta |+_1|+_2|+_3+i\mathrm{sin}\theta |_1|_2|_3,$$
(1)
where $`|+`$ and $`|`$ are the spin-up and down states along the z axis, the subscripts 1,2,3 characterize the three particles. We here assume that $`0<\theta <\pi /4.`$ Consider the physical observables Ei and Ui (i=1,2,3) corresponding to the operators $`\underset{i}{\overset{}{E}}`$ and $`\underset{i}{\overset{}{U}}`$ defined by Eqs. (6) and (7) of Ref. . The Physical quantities Ei and Ui can take 1 or -1 corresponding to the eigenvalues of $`\underset{i}{\overset{}{E}}`$ and $`\underset{i}{\overset{}{U}}.`$ The predictions of quantum mechanics are

$$\text{if }E_1=1\text{ then }U_2U_3=1;$$
(2)
$$\text{if }E_2=1\text{ then }U_1U_3=1;$$
(3)
$$\text{if }E_3=1\text{ then }U_1U_2=1.$$
(4)
Consider a run of measurements, in which predictions (2), (3), and (4) are verified and $`E_1=E_2=E_3=1`$ is obtained. According to local hidden theory, from the result $`E_1=1`$ and (2) one can conclude that if U2 and U3 had been measured one should have obtained $`U_2U_3=1`$. On the other hand, from the result $`E_2=1`$ and (3) one can conclude that if U1 and U3 had been measured one should have obtained $`U_1U_3=1`$. from the result $`E_3=1`$ and (4) one can conclude that if U1 and U2 had been measured one should have obtained $`U_1U_2=1`$. This leads to

$$(U_2U_3)(U_1U_2)(U_1U_3)=1.$$
(5)
However, according to local hidden theory these elements of reality $`U_i`$ have values 1 or -1 and thus $`U_iU_i=1.`$ This will leads to

$$(U_2U_3)(U_1U_2)(U_1U_3)=1.$$
(6)
contradicting with Eq.(5). We thus have revealed the inconsistency hidden in the local hidden variable theory. The self-contraction arises from the assumption that there exists an element of reality corresponding to each Ui even when these quantities are not measured and regardless of what is done to other systems.

Cereceda argued that the above mentioned derivation is not correct . Cereceda claimed that the measurement of $`E_1`$ does not provide any information about the values of $`U_2`$ and $`U_3`$ separately so that elements of reality can not be assigned to $`U_2`$ and $`U_3`$ based on the EPR’s criterion. In fact, Cereceda’s argument is not correct. EPR’s definition of reality is: $`^{^{\prime \prime }}`$If, without in any way disturbing a system, we can predict with certainty (i.e., with probability equal to unity) the value of a physical quantity, then there exists an element of physical reality corresponding to this physical quantity.$`^{^{\prime \prime }}`$ . The measurement of $`E_1=1`$ results in a perfect correlation of $`U_2`$ and $`U_3`$ (i.e., particles 2 and 3 collapse to the maximally entangled state of Eq. (11) of Ref. ). In this case, one can predict with certainty the value to $`U_2`$ ($`U_3`$) by measuring $`U_3`$ ($`U_2`$), without disturbing particle 2(3). Therefore, under the condition $`E_1=1`$, there exist elements of reality corresponding to $`U_2`$ and $`U_3`$ just based on the EPR’s criterion. In the case $`E_1=E_2=E_3=1`$, there exists an element of reality corresponding to each $`U_i`$ based on the EPR’s criterion. Thus, the proof of Ref.  is correct.


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# Effect of Shell Structure on Fission Isoscaling

## Abstract

Recently, the fragment yield ratios were investigated in the fission of 238,233U targets induced by 14 MeV neutrons Veselsky et al. (2003). The effect of the deformed shell structure around N=64 on the dynamics of scission was suggested as an explanation of the observed breakdown of the isoscaling behavior. As an alternative explanation, the effect of binding energy of final fragments, in particular the neutron shell closure of the complementary fragment around N=82, was suggested by Friedman Friedman (2003). When applying that concept consistently, the observed two breakdowns of the isoscaling behavior around N=62 and N=80 signal the effect of two shell closures ( N=82 and N=64 ) on the dynamics of scission. To separate the two effects, we examine the isoscaling plots obtained using fission fragment yield data from the spontaneous fission of the heavier nuclei 248,244Cm and find that the breakdown of isoscaling around N=64 persists even if it can not be related to shell closure of the complementary fragment and thus it manifests the effect of the deformed shell structure in the scission configuration.

Isoscaling phenomena were observed in the isotopic composition of light fragments originating from de-excitation of hot nuclei Tsang et al. (2001) and also in heavy residue data in wide mass range Souliotis et al. (2003). Isoscaling is observed when a ratio of isotope yields from two reactions, differing in isospin asymmetry while other conditions are identical, exhibits an exponential dependence on N and Z of the form $`R_{21}(N,Z)\mathrm{exp}(\alpha N+\beta Z)`$. In our recent study Veselsky et al. (2003), we presented the results of an isoscaling analysis of the fragment yield data from the fission induced by fast neutrons. The evaluated independent fragment yields from the fission of 233,238U targets induced by 14 MeV neutrons England and Rider (1994) were used.

The isoscaling behavior ( Fig. 1 ) was typically observed for isotopic chains ranging from the most proton-rich to most neutron-rich ones. A breakdown of the isoscaling behavior was observed around N=64 which we suggested as a signal of the effect of the deformed shell structure on the dynamics of scission. This can be possibly related to the effect of the deformed neutron shell at N=64 with quadrupole deformation $`\beta _{quad}`$=0.6. According to the fission model of Wilkins et al. Wilkins et al. (1976), this deformed shell closure plays a crucial role in the dynamics of scission. As an alternative explanation, a simple model based on the effect of the binding energy of final fragments was suggested by Friedman Friedman (2003). Assuming Boltzmann statistics with a single temperature for both fragments, the isoscaling yield ratio R21 for a given fragment ($`A_1,Z_1`$) is determined by the Boltzmann factor containing the difference of binding energies of the complementary fragments of the two fissioning systems.

$$R_{lh}(A_1,Z_1)\mathrm{exp}(\frac{\mathrm{\Delta }B_{ld}^{Z_{fiss}Z_1}}{T})\mathrm{exp}(\frac{\mathrm{\Delta }B_{sh}^{Z_{fiss}Z_1}}{T})$$
(1)
where $`\mathrm{\Delta }B_{ld}^{Z_{fiss}Z_1}`$ and $`\mathrm{\Delta }B_{sh}^{Z_{fiss}Z_1}`$ are differences of the liquid-drop and shell structure terms of the binding energies of the complementary fragments with charge $`Z_{fiss}Z_1`$. The binding energies of the liquid drop model ( first factor ) lead to isoscaling behavior while the introduction of shell corrections around N=82 was shown to produce an effect around N=60-65, analogous to the effect observed in the data. The model uses shell corrections derived from the experimental ground state masses and thus corresponding to spherical nuclei. The deformations in the scission configuration are expected to be significant, with exception of mass splits with one fragment around Z=50 which is expected to be spherical Wilkins et al. (1976). The isoscaling behavior obtained when assuming the liquid drop ground state binding energies will possibly not change qualitatively also when deformation will be introduced into the liquid drop model. The effect of deformation on the shell structure can again be expected to lead to isoscaling breakdowns corresponding to deformed shell closures. For the nuclei around N=82, the deformed shell closures are predicted for N=80 and N=88 Wilkins et al. (1976), which may in principle lead to similar effect on isoscaling as the spherical neutron shell N=82. It is worthwile to note that, within the model of Friedman Friedman (2003), the neutron shell N=50 should result in an effect of similar strength in the region around N=94. However, such effect can not be identified unambigiously. On the other hand, the observed breakdown of isoscaling around N=78-80 can be, within the model of Friedman Friedman (2003), explained by the existence of shell closure around N=62-69, where no spherical shell is predicted, which again points to the influence of deformed shell closure around N=64. Thus, the observed behavior supports the presence of the deformed shell around N=64.

As already mentioned, the model framework of Friedman Friedman (2003) is based on the assumption that the probability of a given binary fission channel is determined by a Boltzmann factor depending on the sum of binding energies of two complementary fragments in the scission configuration. The observed data represent the inclusive yields corresponding to various multiplicities of neutrons emitted during fission. The neutron multiplicity distributions are rather wide, even for spontaneous fission Ter-Akopian et al. (1997); Veselsky et al. (1998) and thus the concept of a unique complementary fragment is approximate. The next logical step in the analysis of influence of complementary fragments would be to examine the isoscaling behavior of fissioning systems with different mass. The systematic fission data for nuclei heavier than uranium are rather scarce, one nevertheless can find a good candidate in evaluated independent fragment yield data from spontaneous fission of 248,244Cm England and Rider (1994). The spontaneous fission is a much colder process where additional phenomena such as barrier penetration and potential energy surface can play a crucial role, it is nevertheless interesting to explore it in the context of isoscaling. The isoscaling plot for the spontaneous fission of 248,244Cm is shown in Fig. 2.

In the spontaneous fission of 248,244Cm, the overall isoscaling behavior can be observed from the most populated parts of the mass distribution towards asymmetric mass splits. The breakdowns featuring rather the slope change than the structures observed in the previous case are observed around N=50 and N=62. A strong effect is observed around N=68-70 ( with the complementary fragment around N=82 ), which nevertheless can be a sign of transition into the symmetric region around N=74-76 where the behavior is rather irregular. Furthermore the isoscaling behavior is quite regular up to the heaviest fragments ( with exception of the region around N=94 where a hint of isoscaling breakdown can be observed ). The overall behavior can not be explained using the model of Friedman Friedman (2003) which is logical when assuming that the process is cold and the validity of statistical picture is questionable. It is however remarkable that isoscaling breakdown ( slope change ) is again observed around N=62 ( along with N=50 ). This again possibly points to the role of shell structure, which may influence the potential energy surface and thus the probability of a given fission channel. While around N=50 the shell structure can be identified with a spherical fragment, for the region around N=62 the influence of the deformed shell is the most plausible. The observed isoscaling behavior in the spontaneous fission of 248,244Cm, despite a more complex interpretation, nevertheless again appears to signal the role of the deformed shell closures ( in particluar around N=64 ) in the fission of actinides. Since the isoscaling studies of fission enable to observe details of scission dynamics it is of interest to study the isoscaling behavior within the advanced models of fission, possibly in terms of transport theory, as indicated in Veselsky et al. (2003).


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# Patching up the monopole potential

## Acknowledgment

We would like to thank our colleague Palash Baran Pal for many discussions on . We are also grateful to Amit Ghosh and Parthasarathi Majumdar for several conversations on the subject.