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# Spin quantization axis dependent magnetic properties and x-ray magnetic circular dichroism of FePt and CoPt

## I Introduction

The disordered equiatomic binary alloys of the XY (X= Fe, Co – Y= Pd, Pt) type crystallize in the fcc structure and the magnetization is along the  axis. At low temperatures these alloys tend to order in the $`L1_0`$ layered-ordered structure and in this case the spontaneous magnetization tends to align perpendicular to the layer stacking explaining the behavior of CoPt films during the magnetic annealing. The strong perpendicular magnetic anisotropy (PMA) is due to the highly anisotropic $`L1_0`$ structure and it makes them very attractive for magnetic recording devices. The latter structure can be also obtained by molecular beam epitaxy (MBE) of alternating layers of pure X and Y atoms due to the substrate induced constraints. The first observation of the $`L1_0`$ long-range order for a  CoPt film grown by MBE was made by Harp et al. in 1993 and for a  FePt film by Cebollada et al. Lately other techniques have been also employed to develop films presenting PMA. CoPt films were grown by sputtering by Visokay et al. and by evaporation by Lin and Gorman, and FePt films were grown by various sputtering techniques.

The magneto-crystalline anisotropy energy (MCA) can be probed by many techniques such as torque or ferromagnetic resonance measurements. Both these methods describe the MCA in terms of phenomenological anisotropy constants. It has been demonstrated by Weller et al. that x-ray magnetic circular dichroism (XMCD) is also a suitable technique for probing the MCA, via the determination of the anisotropy of the orbital magnetic moment on a specific shell and site. The x-ray absorption spectroscopy (XAS) using polarized radiation probes element specific magnetic properties of alloys by applying the XMCD sum rules to the experimental spectra. However for itinerant systems, in particular to low symmetry systems, the use of the sum rules is debated because they are derived from an atomic theory. Lately angle-dependent XMCD experiments have been used to provide a deeper understanding for the relation between MCA and the orbital magnetic moments.

The x-ray absorption for CoPt multi-layers has been already studied experimentally by Nakajima et al., Koide et al., Rüegg et al., and Schültz et al. Nakajima et al. revealed a strong enhancement of the cobalt orbital moment when PMA was present, Koide et al. showed that with decreasing cobalt thickness the easy axis rotates from in-plane to out-of-plane, and Rüegg et al. that platinum polarization increases also with decreasing cobalt thickness. Hlil et al. showed by x-ray absorption spectroscopy that modifications of platinum edges in different compounds are correlated to the change in the number of holes.

Several ab-initio calculations have already been performed to investigate the XMCD. The $`L_2`$\- and $`L_3`$-edges involving electronic excitations of 2$`p`$-core electrons towards $`d`$-valence states have primarily attracted much attention due to dependence of the dichroic spectra on the exchange-splitting and the spin-orbit coupling of both initial core and final valence states. For 5$`d`$ elements dissolved in 3$`d`$ transition metals, the spin-orbit coupling of the initial 2$`p`$-core states is large and the resulting magnetic moment is small, while the opposite is true for the 3$`d`$ elements. This can lead to a pronounced dichroic spectra as seen by Schütz in the case of 5$`d`$ elements dissolved in iron.

In this work we study the correlation between the quantization axis dependent XMCD and the magnetic properties of both ordered alloys FePt and CoPt. Our method is based on an all-electron relativistic and spin-polarized full-potential muffin-tin orbital method (LMTO) in conjunction with both the von Barth and Hedin parameterization to the local density approximation (LSDA) and the generalized gradient approximation (GGA) to the exchange correlation potential. The implementation of the calculation of the XMCD spectra has been presented in a previous work. In section 2 we present the details of the calculations, while in sections 3 and 4 we discuss our MCA and the magnetic spin and orbital moments, respectively. In section 5 we present our calculated XMCD as a function of the spin quantization axis, and in section 6 we discuss the interpretation of the MCA using the band structure and the total density of states anisotropy.

## II Computational Details

To compute the electronic properties of CoPt and FePt we used the experimental lattice constants ($`a`$=3.806Å and $`c`$/$`a`$=0.968 for CoPt; $`a`$= 3.861Å and $`c`$/$`a`$=0.981 for FePt) and a unit cell containing one atom of cobalt(iron) and one of platinum. The $`L1_0`$ structure can be seen as a system of alternating cobalt(iron) and platinum layers along the  direction. The MCA and the XMCD are computed with respect to the angle $`\gamma `$ between the  axis and the spin quantization axis on the (010) plane. So $`\gamma `$=0o corresponds to the  axis and $`\gamma `$=90o to the  axis.

MCA can be computed directly using ab-initio methods; it is defined as the difference between the total energy for two different spin quantization axis. The spin-orbit coupling contribution to MCA is implicitly included in our ab-initio calculations, and we do not take into account the many-body interactions of the spin-magnetic moments since their contribution to the MCA is negligible. The number of k points for performing the Brillouin zone (BZ) integration depends strongly on the interplay between the contributions to the MCA from the Fermi surface and the remaining band structure contribution to the total energy. When the former contribution to the MCA is important, a large number of k-points is needed to describe accurately the Fermi surface. For the two studied systems we found that 6750 k-points in the BZ are enough to converge the MCA within 0.1 meV.

To perform the integrals over the BZ we use a Gaussian broadening method which convolutes each discrete eigenvalue with a Gaussian function of width 0.1 eV. This method is known to lead to a fast and stable convergence of the spin and charge densities compared to the standard tetrahedron method. To develop the potential inside the MT spheres we calculated a basis set of lattice harmonics including functions up to $`\mathrm{}=8`$, while for the FFT we used a real space grid of 16$`\times `$16$`\times `$20. We used a double set of basis functions, one set to describe the valence states and one for the unoccupied states. For the valence electrons we used a basis set containing 3$`\times s`$, 3$`\times p`$ and 2$`\times d`$ wave functions, and for the unoccupied states 2$`\times s`$, 2$`\times p`$ and 2$`\times d`$ wave functions.

## III Magneto-crystalline Anisotropy

CoPt and FePt films are known to present a strong uniaxial MCA, because of the high anisotropic $`L1_0`$ inter-metallic phase. Experimentally the magnetization axis is found to be along the  direction. In a first step we performed calculations with 250 k-points in the BZ. This number of k-points is large enough to produce accurate total energy when Gaussian smearing is used for the integration in the Brillouin Zone but not enough accurate to compute the MCA. In figure 1 we present calculations with respect to the angle $`\gamma `$ between the  axis and the spin quantization axis on the (010) plane for the CoPt compound within the LSDA. We observe that total energy value increases with the angle $`\gamma `$. So the ground state corresponds to $`\gamma `$=0o, i.e. the  axis. The same behavior occurs for the FePt compound. Because 250 k-points are not enough to produce an accurate value for the MCA, we present in figure 2 the convergence of the MCA with the number of k-points for both compounds within LSDA. The MCA is the difference in the total energy between the in-plane axis  and  and the easy axis . We have found that the total energy difference between the  and the  directions is negligible compared to the difference between the in-plane axis and the  axis. Our values are converged up to 6750 k-points and are given per unit cell (one atom of X and one of platinum). The MCA converges to 2.2 eV for CoPt and 3.9 eV for FePt. These behavior confirms the assumption that the system is isotropic inside the plane. The GGA MCA calculations converged to 1.9 meV and 4.1 meV for CoPt and FePt, respectively. The GGA results seem to be in good agreement with the LSDA results.

Daalderop et al. performed calculations for MCA in CoPt and FePt by means of an LMTO method in the atomic sphere approximation (ASA) within LSDA using the force theorem. The easy magnetization axis found by this latter calculation is the  for both systems in agreement with our LSDA and GGA results. Their MCA value is 2 meV for CoPt and is 3.5 meV for FePt. Solovyev et al. used the same structure within a real-space Green’s function technique framework to find also that the magnetization is along the  axis. Including the spin-orbit interaction for all the atoms, they found a CoPt MCA value of 2.3 meV and a FePt value of 3.4 meV. Our computed value agrees also with the value of 1.5 meV for CoPt and 2.8 meV for FePt, obtained by Sakuma using LMTO method in the atomic sphere approximation (ASA) in conjunction with the force theorem. The drawback of the LMTO-ASA method is that it accounts only for the spherical part of the potential and ignores the interstitial region. Furthermore, the force theorem does not account directly for the exchange-correlation contribution to the MCA. Finally, Oppeneer used the augmented spherical waves method (ASW) in the atomic sphere approximation and found a MCA value of 2.8 meV for FePt and 1.0 meV for CoPt, which are the smallest among all the ab-initio calculations.

Grange et al., using a torque measurement for a MBE deposited CoPt film on a MgO(001) substrate, obtained a MAE of 1.0 meV. An early measurement of a monocristal of CoPt, by Eurin and Pauleve, produced a value of 1.3 meV. The large value of Eurin and Pauleve is due to the fact that their sample was completely ordered. For FePt the first experiment of Ivanov et al. produced an anisotropy value of 1.2 meV and showed that for a thin film the shape anisotropy would be one order of magnitude smaller compared to the MCA. Farrow et al. and Thiele et al. found for MBE deposited FePt films on a MgO(001) substrate an anisotropy value of 1.8 meV. These films were highly ordered (more than 95% of the atoms were in the correct site). All experiments have been carried out at room temperature, which explain at some extend the difference between the calculated and experimental MCA values (the MCA decreases with temperature). It is worth mentioning that the experimental MCA for FePt is much larger than that of CoPt in agreement with our calculations. For thick films volume shape anisotropy (VSA) contributes also to the MAE and it favors always an in-plane magnetization axis. We can estimate the VSA as $`2\pi M_V^2`$ in c.g.s. units, where $`M_V`$ is the mean magnetization density, and obtain a value of -0.1 meV for FePt and -0.06 meV for CoPt. These values are one order of magnitude smaller than the MCA values in agreement with the speculation of Ivanov et al.

## IV Magnetic moments

### A Density of States

In figure 3 we present the cobalt-projected partial density of states for three spin quantization axis corresponding to angles $`\gamma `$= 0o, 45o and 90o calculated with 6750 k-points. The 3-$`d`$ states dominate the electronic structure of cobalt. The spin-up band is practically totally occupied while the spin down band is almost half-occupied. The general form of the cobalt DOS, as well as the iron DOS, does not seem to change appreciably with the angle $`\gamma `$. The platinum projected density of states show similar behavior for both FePt and CoPt compounds. Bulk platinum is paramagnetic and the small changes in the DOS come from the polarization of the 5$`d`$ electrons via hybridization with the 3$`d`$ electrons of cobalt (iron). It is worth mentioning that the DOS is calculated inside each muffin-tin and the interstitial region is not taken into account. To minimize the contribution of the interstitial region we use almost touching muffin-tin spheres. In addition, we have find that remaining region has a negligible spin polarization.

### B Spin Magnetic Moments

The spin magnetic moments are isotropic with respect to the spin quantization axis as expected. They were calculated by attributing all the charge inside each muffin-tin sphere to the atom located in that sphere. As outlined above we have found that the interstitial contribution to the spin magnetic moment is one order of magnitude smaller than that of the platinum site. In CoPt we found a cobalt spin magnetic moment of 1.79 $`\mu _B`$ and a platinum moment of 0.36 $`\mu _B`$ within the LSDA. The GGA cobalt spin magnetic moment of 1.83 $`\mu _B`$ is slightly larger than the value within LSDA. This is due to a more atomic like description of the atoms in a solid within the GGA compared to the LSDA. Although the GGA underestimates the hybridization between cobalt and platinum $`d`$ valence electrons compared to the LSDA, the larger cobalt spin moment leads to a slightly larger GGA platinum spin moment of 0.37 $`\mu _B`$. Our calculated values are in good agreement with the experimental values of Grange et al. (1.75$`\mu _B`$ for cobalt and 0.35$`\mu _B`$ for platinum). Previous experiments by van Laar on a powder sample gave a value of 1.7 $`\mu _B`$ for the cobalt atom and 0.25 for the platinum atom. The spin magnetic moments have been previously calculated by Solovyev et al. (1.72 for cobalt and 0.37 for platinum), by Daalderop et al (1.86 for cobalt), by Sakuma (1.91 for cobalt and 0.38 for platinum), and finally by Kootte et al. by means of a localized spherical wave method (1.69 for cobalt and 0.37 for platinum). All previous calculations are in good agreement with our full-potential results.

As expected the iron spin moments are much larger than the cobalt ones. The LSDA produced a value of 2.87 $`\mu _B`$ while the GGA produced a slightly larger value, 2.96 $`\mu _B`$. The hybridization between the iron 3$`d`$ states and the platinum 5$`d`$ states is less intense than in the case of CoPt resulting in a smaller platinum moment for FePt. The LSDA platinum spin moment is 0.33 $`\mu _B`$ (compared to 0.36 $`\mu _B`$ in CoPt) and the GGA platinum spin moment is 0.34 $`\mu _B`$ (compared to 0.37 $`\mu _B`$ in CoPt). The spin magnetic moments have been previously calculated by Solovyev et al (2.77 for iron and 0.35 for platinum), by Daalderop et al (2.91 for iron), by Sakuma (2.93 for iron and 0.33 for platinum), and finally by Osterloch et al. (2.92 for iron and 0.38 for platinum). Here again all previous calculations are in good agreement with our full-potential results. All the methods produced a smaller induced spin moment for platinum atom in FePt than for CoPt, verifying that the hybridization effect in CoPt is much stronger than in FePt.

### C Orbital Magnetic Moments

Contrary to spin moments, the orbital moments are anisotropic. Figure 4 presents the behavior of the orbital moments as a function of the angle $`\gamma `$ between the  direction and the spin quantization axis within LSDA for both CoPt and FePt compounds (the lines are guide to the eye). The orbital moments decrease with respect to the angle $`\gamma `$ but the values for the  axis does not follow this general trend. All four lines seem to have the same behavior, but it is interesting to notice that for the CoPt and magnetization along the  axis cobalt orbital moment is smaller than the platinum one (for the values see Tables I and II). The cobalt moments decrease faster than platinum moments in CoPt. For the iron and platinum atoms in FePt the two lines are practically parallel. The platinum orbital moments in FePt are smaller than for the CoPt with a factor that varies from 73% for $`\gamma `$=0o to 67% for $`\gamma `$=90o. The ratio of iron and platinum orbital moments in FePt varies from 1.56 for $`\gamma `$=0o down to 1.35 for for $`\gamma `$=90o, which is considerably smaller than the ratio of cobalt and platinum orbital moments in CoPt. We notice here that in our calculations we can estimate only the projection of the total orbital moment on the spin quantization axis and we have no information concerning the real value of the total magnetic moment or its direction in space. It seems that for the magnetization along the  direction, the direction of the orbital magnetic moment undergoes a discontinuous jump, resulting in a large projection on the spin quantization axis with respect to $`\gamma `$ at the vicinity of 90o. This behavior is also reproduced by the GGA.

In Table I we present the values of the orbital moments of iron and cobalt within both the LSDA and GGA as a function of the angle $`\gamma `$. The GGA values seem to be smaller than the LSDA ones but follow exactly the same trends. The orbital moment anisotropy is more important in the case of cobalt. The LSDA cobalt orbital moment changes by 0.048 $`\mu _B`$ and the GGA moment by 0.027 $`\mu _B`$ as we pass from the easy axis  to the hard axis . The LSDA iron moment changes by 0.002 $`\mu _B`$ and the GGA moment is the same for the two high symmetry directions. In the case of cobalt the difference between values calculated within the two functionals, LSDA and GGA, becomes smaller when the angle increases and for 75o it changes sign. In the case of iron this difference decreases only slightly with the angle but since the difference is considerably smaller than in CoPt (less than 0.004), we conclude that the orbital moment in the LSDA and the GGA are roughly the same.

In Table II we present the values for the platinum orbital moment within both functionals. We see that the GGA produces larger moments than the LSDA for platinum in FePt contrary to CoPt. The platinum moments are in general smaller than the moments of the 3$`d`$ ferromagnets, and the difference between the values calculated within LSDA and GGA are small. The absolute values for platinum are comparable to cobalt(iron) orbital moments even though the spin moments on platinum are one order of magnitude smaller than for cobalt(iron). The large orbital moments for platinum are due to a much larger spin-orbit coupling for the $`d`$ electrons of the platinum compared to the 3$`d`$ ferromagnets.

The orbital moments of FePt and CoPt have been previously calculated by Daalderop and collaborators and by Solovyev and collaborators for the  direction using the LSDA. The orbital moment of the cobalt site was found to be 0.12 $`\mu _B`$ by Daalderop and 0.09 $`\mu _B`$ by Solovyev. The value of Daalderop is closer to our LSDA value of 0.11 $`\mu _B`$. For iron site Daalderop found a value of 0.08 $`\mu _B`$ and Solovyev 0.07 $`\mu _B`$ in good agreement with our LSDA value. The platinum orbital moment has been calculated by Solovyev. He found a value of 0.06 $`\mu _B`$ for platinum in CoPt and 0.044 $`\mu _B`$ for platinum in FePt, close to our values, 0.06 $`\mu _B`$ and 0.05 $`\mu _B`$, respectively.

On the other hand, experimental data are available for CoPt by Grange; obtained by applying the sum rules to the experimental XMCD spectra. The sum rules give the moments per hole in the $`d`$-band. To compare experiment with theory we calculated the number of $`d`$-holes by integrating the $`d`$ projected density of states inside each muffin-tin sphere. We found 2.63 $`d`$ and 2.48 $`d`$ holes for cobalt and platinum, respectively. The cobalt orbital moment varies from 0.26 $`\mu _B`$ for $`\gamma `$=10o down to 0.11 $`\mu _B`$ for $`\gamma `$=60o. The measured values are also available for two other angles: 0.24 $`\mu _B`$ for $`\gamma `$=30o and 0.17 $`\mu _B`$ for $`\gamma `$=45o. Our theory reproduces qualitatively the experimental trends but underestimates the absolute values by more than 50% (see Tables I and II for all the values). The calculated values show a less sharp decrease with the angle than the experimental ones. For platinum the experimental data are available only for two angles 10o and 60o. For $`\gamma `$=10o the orbital moment is 0.09 $`\mu _B`$ and for $`\gamma `$=60o it is 0.06 $`\mu _B`$. For the platinum site the calculated values are in much better agreement than for the cobalt site but we must keep in mind that the sum rules have their origin in an atomic theory and their use for 5$`d`$ itinerant electrons like in platinum is still debated. The discrepancy between the theory and the experiment comes mainly from the approximation to the exchange and correlation. Both the LSDA and the GGA approximations to the density functional theory are known to underestimate the orbital moment values, because the orbital moment is a property directly associated with the current in the solid and a static image is not sufficient. But until now a DFT formalism like the current and spin density functional theory (CS-DFT), which can treat at the same footing the Kohn-Sham and the Maxwell equations is too heavy to implement in a full-potential ab-initio method. The other problem is that there is no form of the exchange energy of a homogeneous electronic gas in a magnetic field known and this is the main quantity entering the CS-DFT formalism. Brooks has also developed an ad hoc correction to the Hamiltonian to account for the orbital polarization but this correction originates from an atomic theory and its application to itinerant systems is not satisfactory.

## V XMCD

XMCD spectroscopy became popular after the development of the sum rules that enable the extraction of reliable information on the micro-magnetism directly from the experimental spectra. The great advantage of XMCD is that we can probe each atom and orbital in the system so to obtain information on the local magnetic properties. Lately angle-dependent XMCD experiments allowed the determination of magnetic properties for different spin quantization axis. All experimental spectra for CoPt have been obtained by Grange et al, and all calculated spectra presented in this section were obtained using the LSDA. The GGA produced the same results and are not presented.

Figure 5 presents the XMCD spectra for cobalt and iron atoms for the  and  magnetization axis. We convoluted our theoretical spectra using a Lorentzian width of 0.9 eV and a Gaussian width of 0.4 eV as proposed by Ebert, in the case of iron to account for the core hole effect and the experimental resolution, respectively. The energy difference between the $`L_3`$ and $`L_2`$ peaks is given by the spin-orbit splitting of the $`p_{\frac{1}{2}}`$ and $`p_{\frac{3}{2}}`$ core states. It is larger in the case of cobalt, 14.8 eV, than for iron, 12.5 eV. The intensities of the peaks are comparable for both atoms, but the cobalt peak-intensities are larger for the  axis contrary to the iron spectrum. The most important feature of these spectra is the integrated $`L_3`$/$`L_2`$ branching ratio as it enters the sum rules. It is larger in the case of cobalt site. This is expected since the sum rules predict that a larger $`L_3`$/$`L_2`$ ratio is equivalent to a larger orbital moment. For both atoms the integrated $`L_3`$/$`L_2`$ branching ratio is larger for the  axis. But the ratio anisotropy is larger for the cobalt site (1.32 for M$``$ and 1.17 for M$``$) than for the iron site (1.15 for M$``$ and 1.14 for M$``$) reflecting the larger orbital moment anisotropy of cobalt compared to iron (see Table I). Especially for iron both orbital moment and integrated $`L_3`$/$`L_2`$ branching ratio are practically the same for both magnetization axis. As these changes in the XMCD signal are related to the change in the orbital magnetic moment between the two magnetization directions. The XMCD anisotropy should be roughly proportional to the underlying MCA but no relation exist that connects these two anisotropies. However they are connected indirectly through the orbital moment anisotropy.

In figure 6 we have plotted the platinum XMCD spectra for two angles $`\gamma `$=10o and 60o for both compounds. The life time of the core-hole in platinum is smaller than for cobalt so the broadening used to account for its life time should be larger. We used both a Lorentzian (1 eV) and a Gaussian (1 eV) to represent this life time and a Gaussian of 1 eV width for the experimental resolution. As in the case of cobalt and iron the platinum XMCD spectra change with the angle and depend on the surrounding neighbors. The peak intensities are larger in CoPt. Also the difference in the intensity due to the anisotropy has different sign in the two compounds. The intensities of FePt spectra for $`\gamma `$=10o are much larger than for $`\gamma `$=60o contrary to the CoPt behavior. As is the case for cobalt in CoPt, the platinum site integrated $`L_3`$/$`L_2`$ branching ratio shows larger anisotropy than for platinum in FePt. In CoPt it is 1.49 for $`\gamma `$=10o and 1.19 for $`\gamma `$=60o, while for FePt it is 1.20 for $`\gamma `$=10o and 1.14 for $`\gamma `$=60o. Here again the XMCD follows the anisotropy of the orbital magnetic moment in these compounds. The energy difference between the two peaks is 1727 eV for both compounds. The 2$`p`$ electrons of platinum are deep in energy and are little influenced by the local environment, so that their spin-orbit splitting does not depend on the neighboring atoms of platinum.

We expect a better agreement between the theoretical and the experimental XMCD spectra for the platinum site than for the cobalt site, because the core hole is deeper and would effect less the final states of the photo-excited electron. In figure 7, we have plotted the absorption and the XMCD spectra of cobalt for $`\gamma `$=0o. We have scaled our spectra in a way that the experimental and theoretical $`L_3`$ peaks in the absorption spectra have the same intensity. The energy difference between the $`L_3`$ and $`L_2`$ peaks is in good agreement with experiment. But the intensity of the $`L_2`$ peak is larger than the corresponding experimental peak. The high intensity of the calculated $`L_2`$ edge makes the theoretical XMCD integrated $`L_3`$/$`L_2`$ branching ratio of 1.32 much smaller than the experimental ratio of 1.72. This is because the LSDA fails to represent the physics of the core hole photo-excited electron recombination. In the case of 3$`d`$ ferromagnets the core hole is shallow and influences the final states seen by the photo-excited electron. A formalism that can treat this electron-hole interaction has been proposed by Schwitalla and Ebert, but it failed to improve the $`L_3`$/$`L_2`$ branching ratio of XAS of the late transition metals. Benedict and Shirley have also developed a scheme to treat this phenomena but its application is limited only to crystalline insulators.

In figure 8 we have plotted experimental and theoretical total absorptions for the platinum atom in CoPt. For both $`L_2`$ and $`L_3`$ edges the theory gives a sharp peak which does not exist in experiment. As expected the $`L_3`$ peak is much more intense than the $`L_2`$. In contrast to what is obtained for cobalt, the results for the platinum XMCD (see figure 9) show better agreement with experiment, due to the fact that the core hole effect is less intense (core hole much deeper compared to cobalt). The experimental and theoretical $`L_2`$ and $`L_3`$ edges are separated by a spin-orbit splitting of the $`2p`$ core states of 1709 and 1727eV respectively. The width of both $`L_2`$ and $`L_3`$ edges is comparable to experiment, but the calculated $`L_2`$ edge is much larger. This produces a calculated integrated branching ratio of 1.49 which is much smaller than the experimental ratio of 2.66. Here again the theory is underestimating the branching ratio.

## VI Band Structure and Density of States Anisotropy

In figure 10 we present the band structure along the  and  axis in the reciprocal space for different angles $`\gamma `$ for the CoPt compound within the LSDA. We know that it is essentially the area around the Fermi level that changes with respect to the spin quantization axis. For this reason we have enlarged a region of $`\pm `$1 eV around the Fermi level. In the first panel we plot the relativistic band structure for $`\gamma `$=0o. In the second and third panel we have plotted the relativistic band structure for $`\gamma `$=45o and $`\gamma `$=90o. We remark that as the angle increases there are bands that approach the Fermi level and cross it. However this information concerns just two high symmetry directions. For this reason we limited ourselves to the changes in the total DOS. In figure 11 we notice that just below the Fermi level the DOS for the hard axis is lower than for the easy axis which seems to favor the hard axis. This means that the anisotropy does not originate from the changes ate the vicinity of the Fermi level but from that of the whole DOS. It is difficult to investigate this phenomena by inspection of the changes at the vicinity of the Fermi surface and to explain the sign of the MCA . Our results confirm the work of Daalderop and collaborators that argued that not only states in the vicinity of the Fermi surface contribute to the MAE, as originally thought, but states far away make an equally important contribution.

## VII Conclusion

We have performed a theoretical ab-initio study of the magnetic properties of the ordered CoPt and FePt fct alloys systems. The calculated easy axis is the  for both compounds in agreement with other calculations and with experiments on films which found a strong perpendicular magnetization axis. The density of states is found to change very little with the direction of the spin quantization axis, and hence the magnetic moments are isotropic with respect to the magnetization axis. Contrary to the spin moments, the orbital magnetic moments decrease with the angle $`\gamma `$ up to 75o ($`\gamma `$ is the angle between the spin quantization axis and the  axis).

The calculated x-ray magnetic circular dichroism (XMCD) for all the atoms reflect the behavior of the orbital moments. Especially platinum resolved spectra present large differences between the two compounds. Cobalt XMCD spectra are in agreement with experiment but as usual the $`L_3`$/$`L_2`$ ratio is underestimated by the theory. The platinum site shows better agreement with experiments because the core-hole is much deeper than in the case of cobalt.

Finally we showed that all the occupied electronic states contribute to the magneto-crystalline anisotropy and not just states near the Fermi level for both CoPt and FePt.

## Acknowledgments

We thank J. M. Wills for providing us with his FPLMTO code. I.G. is supported by an European Union grant No ERBFMXCT96-0089. The calculations were performed using the SGI Origin-2000 supercomputer of the Université Louis Pasteur de Strasbourg and the IBM SP2 supercomputer of the CINES under grant gem1917.


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# The masses of the mesons and baryons. Part I. The integer multiple rule

## 1 The spectrum of the masses of the particles

The masses of the elementary particles are the best-known and most characteristic property of the particles. It seems to be important for the theoretical explanation of the masses of the particles to find a simple relationship between the different masses, as the formula for the Balmer series was important for the explanation of the spectrum of hydrogen. We will limit attention here to the mesons and baryons all of which are unstable, but for the proton. However, the lifetime of the mesons and baryons is so long as compared to the period of the basic frequency $`\nu =mc^2/h`$ that the mesons and baryons have often been categorized as “stable” or “elementary” particles. The masses of the so-called “stable” mesons and baryons are given in the “Particle Physics Summary” , and are reproduced with other data in Tables I,II.

It is obvious that any attempt to explain the masses of the elementary particles should begin with the particles that are affected by the fewest parameters. These are certainly the particles without isospin ($`I=0`$) and without spin ($`J=0`$), but also with strangeness $`S=0`$, and charm $`C=0`$. Looking at the particles with $`I,J,S,C=0`$ it is startling to find that their masses are quite close to integer multiples of the mass of the $`\pi ^0`$ meson. It is $`m(\eta )=(1.0140\pm 0.0003)4m(\pi ^0)`$, and $`m(\eta ^{})=(1.0137\pm 0.00015)7m(\pi ^0)`$. We also note that the average mass ratios $`[m(\eta )/m(\pi ^0)+m(\eta )/m(\pi ^+)]/2=3.9892=0.99734`$, and $`[m(\eta ^{})/m(\pi ^0)+m(\eta ^{})/m(\pi ^+)]/2=6.9791=0.99707`$ are good approximations to the integers 4 and 7. Three particles seem hardly to be sufficient to establish a rule. However, if we look a little further we find that $`m(\mathrm{\Lambda })=1.03328m(\pi ^0)`$ or $`m(\mathrm{\Lambda })=1.01902m(\eta )`$. We note that the $`\mathrm{\Lambda }`$ particle has spin $`\frac{1}{2}`$, not spin 0 as the $`\pi ^0`$, $`\eta `$, $`\eta ^{}`$, mesons. Nevertheless, the mass of $`\mathrm{\Lambda }`$ is close to $`8m(\pi ^0)`$. Furthermore we have $`m(\mathrm{\Sigma }^0)=0.98179m(\pi ^0)`$, $`m(\mathrm{\Xi }^0)=0.974210m(\pi ^0)`$, $`m(\mathrm{\Omega }^{})=1.032512m(\pi ^0)=1.01833m(\eta )`$, ($`\mathrm{\Omega }^{}`$ is charged and has spin $`\frac{3}{2}`$). Finally the masses of the charmed baryons are $`m(\mathrm{\Lambda }_c^+)=0.995817m(\pi ^0)=1.023216m(\pi ^+)=1.0242m(\mathrm{\Lambda })`$, $`m(\mathrm{\Sigma }_c^0)=1.009318m(\pi ^0)`$, $`m(\mathrm{\Xi }_c^0)=1.016718m(\pi ^0)`$, and $`m(\mathrm{\Omega }_c^0)=1.001720m(\pi ^0)`$. Now we seem to have enough material to formulate the integer multiple rule, according to which the masses of the $`\eta `$, $`\eta ^{}`$, $`\mathrm{\Lambda }`$, $`\mathrm{\Sigma }^0`$, $`\mathrm{\Xi }^0`$, $`\mathrm{\Omega }^{}`$, $`\mathrm{\Lambda }_c^+`$, $`\mathrm{\Sigma }_c^0`$, $`\mathrm{\Xi }_c^0`$ and $`\mathrm{\Omega }_c^0`$ particles are, in a first approximation, integer multiples of the mass of the $`\pi ^0`$ meson, although some of the particles have spin, and may also have charge as well as strangeness and charm. A consequence of the integer multiple rule must be that the ratio of any meson or baryon mass divided by the mass of another meson or baryon is equal to the ratio of two integer numbers. And indeed, for example, $`m(\eta )/m(\pi ^0)`$ is practically two times (exactly $`0.99502`$) the ratio $`m(\mathrm{\Lambda })/m(\eta )`$, there is also the ratio $`m(\mathrm{\Omega }^{})/m(\mathrm{\Lambda })=0.9993\frac{3}{2}=0.99931.5`$. We have furthermore the ratios $`m(\mathrm{\Lambda })/m(\eta )=1.0192`$, $`m(\mathrm{\Omega }^{})/m(\eta )=1.0183`$, $`m(\mathrm{\Lambda }_c^+)/m(\mathrm{\Lambda })=1.023992`$, $`m(\mathrm{\Sigma }_c^0)/m(\mathrm{\Sigma }^0)=1.02812`$, and $`m(\mathrm{\Omega }_c^0)/m(\mathrm{\Xi }^0)=1.02822`$.

We will call, for reasons to be explained later, the particles discussed above, which follow in a first approximation the integer multiple rule, the $`\gamma `$-branch of the particle spectrum. The mass ratios of these particles are listed in Table I. The deviation of the mass ratios from exact integer multiples of $`m(\pi ^0)`$ is at most 3.3%, the average of the factors in front of the integer multiples of $`m(\pi ^0)`$ of the ten $`\gamma `$-branch particles in Table I is $`1.0073\pm 0.0184`$. From a least square analysis follows that the masses of the eleven particles on Table I obey the formula $`m=1.0059N+0.0074`$ with a correlation coefficient $`r=0.999`$. The consequences of the combination of spin, isospin, strangeness and charm are difficult to assess. Nevertheless, even the combination of four different parameters does not change the integer multiple rule by more than 3.3%. To put this into perspective we note that the masses of the $`\pi ^\pm `$ mesons and the $`\pi ^0`$ meson differ already by 3.4%.

Spin seems to have a profound effect on the mass of a particle. Changing the spin from zero for the $`\pi ^0`$, $`\eta `$, $`\eta ^{}`$, mesons to spin $`\frac{1}{2}`$ for the $`\mathrm{\Lambda }`$ baryon is accompanied by a mass twice the mass of the $`\eta `$ meson, it is $`m(\mathrm{\Lambda })=1.01902m(\eta )`$. The isospins of $`\eta `$ and $`\mathrm{\Lambda }`$ are both zero. The change of $`S`$ and the baryon number $`B`$ which accompany the formation of $`\mathrm{\Lambda }`$ seems to have little effect on the mass of the $`\mathrm{\Lambda }`$ particle and the other baryons, as follows from the masses of the baryons whose $`S`$ changes from $`1`$ to $`3`$. We find it most interesting that spin $`\frac{3}{2}`$ is accompanied with a mass three times $`m(\eta )`$, the $`\mathrm{\Omega }^{}`$ particle; whereas spin $`\frac{1}{2}`$ is accompanied by a mass two times $`m(\eta )`$, the $`\mathrm{\Lambda }`$ particle.

Searching for what the $`\pi ^0`$, $`\eta `$, $`\eta ^{}`$, $`\mathrm{\Lambda }`$, $`\mathrm{\Sigma }^0`$, $`\mathrm{\Xi }^0`$, $`\mathrm{\Omega }^{}`$ particles have else in common, we find that the principal decays (decays with a fraction $`>1`$%) of these particles, as listed in Table I, involve primarily $`\gamma `$’s, the characteristic case is $`\pi ^0\gamma \gamma `$ (98.8%). The next most frequent decay product of the heavier particles of the $`\gamma `$-branch are $`\pi ^0`$ mesons which again decay into $`\gamma \gamma `$. To describe the decays in another way, the principal decays of the particles listed above take place always without the emission of neutrinos; see Table I. There the decays and the fractions of the principal decay modes are listed, as they are given in the Particle Physics Summary. We cannot consider decays with fractions $`<1`$%. We will refer to the particles whose masses are approximately integer multiples of the mass of the $`\pi ^0`$ meson, and which decay without the emission of neutrinos, as the $`\gamma `$-branch of the particle spectrum.

To summarize the facts concerning the $`\gamma `$-branch. Within about 3% the masses of the particles of the $`\gamma `$-branch are integer multiples (namely 4, 7, 8, 9, 10, 12, and even 17, 18, 20) of the mass of the $`\pi ^0`$ meson. It is improbable that nine particles have masses so close to integer multiples of $`m(\pi ^0)`$ if there is no correlation between them and the $`\pi ^0`$ meson. It has, on the other hand, been argued that the integer multiple rule is a numerical coincidence. But the probability that the mass ratios of the $`\gamma `$-branch fall by coincidence on integer numbers between 1 and 20 instead on all possible percentage values between 1 and 20 is smaller than $`10^{20}`$, i.e., nonexistent. The integer multiple rule is not affected by more than 3% by the spin, the isospin, the strangeness, and by charm. The integer multiple rule seems even to apply to the $`\mathrm{\Omega }^{}`$ and $`\mathrm{\Lambda }_c^+`$ particles, although they are charged. In order for the integer multiple rule to be valid the deviation of the ratio $`m/m(\pi ^0)`$ from an integer number must be smaller than $`1/2N`$, where $`N`$ is the integer number closest to the actual ratio $`m/m(\pi ^0)`$. That means that the permissible deviation decreases rapidly with $`N`$. All particles of the $`\gamma `$-branch have deviations smaller than $`1/2N`$.

The remainder of the stable mesons and baryons are the $`\pi ^\pm `$, $`K^{\pm ,0}`$, $`p`$, $`n`$, $`D^{\pm ,0}`$ and $`D_S^\pm `$ particles. These are in general charged, exempting the $`K^0`$ and $`D^0`$ mesons and the neutron $`n`$, in contrast to the particles of the $`\gamma `$-branch, which are in general neutral. It does not make a significant difference whether one considers the mass of a particular charged or neutral particle. After the $`\pi `$ mesons, the largest mass difference between charged and neutral particles is that of the $`K`$ mesons (0.81%), and thereafter all mass differences between charged and neutral particles are $`<0.5`$%. The integer multiple rule does not immediately apply to the masses of the charged particles if $`m(\pi ^\pm )`$ (or $`m(\pi ^0)`$) is used as reference, because $`m(K^\pm )=0.88434m(\pi ^\pm )`$. $`0.88434`$ is far from integer. Since the masses of the $`\pi ^0`$ meson and the $`\pi ^\pm `$ meson differ by only 3.4% it has been argued that the $`\pi ^\pm `$ mesons are, but for the isospin, the same particles as the $`\pi ^0`$ mesons, and that therefore the $`\pi ^\pm `$ cannot start another particle branch. However, this argument is not supported by the completely different decays of the $`\pi ^0`$ mesons and the $`\pi ^\pm `$ mesons. The $`\pi ^0`$ meson decays almost exclusively into $`\gamma \gamma `$ (98.8%), whereas the $`\pi ^\pm `$ mesons decay practically exclusively into $`\mu `$-mesons and neutrinos, e.g. $`\pi ^+\mu ^++\nu _\mu `$ (99.987%). Furthermore, the lifetimes of the $`\pi ^0`$ and the $`\pi ^\pm `$ mesons differ by nine orders of magnitude, being $`\tau (\pi ^0)=8.410^{17}`$ sec versus $`\tau (\pi ^\pm )=2.610^8`$ sec.

If we make the $`\pi ^\pm `$ mesons the reference particles of the $`\nu `$-branch, then we must multiply the mass ratios $`m/m(\pi ^\pm )`$ of the above listed particles with a factor $`0.861\pm 0.022`$, as follows from the mass ratios listed on Table II. The integer multiple rule may, however, apply directly if one makes $`m(K^\pm )`$ the reference for masses larger than $`m(K^\pm )`$. The mass of the proton is $`0.95032m(K^\pm )`$, which is only a fair approximation to an integer multiple. There are, on the other hand, outright integer multiples in $`m(D^\pm )=0.99612m(p)`$, and in $`m(D_S^\pm )=0.99684m(K^\pm )`$. We note that the spin $`\frac{1}{2}`$ of the proton is associated with a mass twice the mass of the spinless $`K`$ meson, just as it was with the spin of the $`\mathrm{\Lambda }`$ particle, which is associated with a mass twice the mass of the spinless $`\eta `$ meson. We note further that the spin of the $`D^\pm `$ mesons, whose mass is nearly $`2m(p)`$, is zero, whereas the spin of the proton is $`\frac{1}{2}`$. It appears that the superposition of two particles of the same mass and with spin $`\frac{1}{2}`$ can cancel the spin. On the other hand, it appears that the superposition of two particles of equal mass without spin can create a particle with spin $`\frac{1}{2}`$.

Contrary to the particles of the $`\gamma `$-branch, the charged particles decay preferentially with the emission of neutrinos, the foremost example is $`\pi ^+\mu ^++\nu _\mu `$ with a fraction of 99.987%. Neutrinos characterize the weak interaction. We will refer to the charged particles listed in Table II as the neutrino branch ($`\nu `$-branch) of the particle spectrum. We emphasize that a weak decay of the particles of the $`\nu `$-branch is by no means guaranteed, the proton is stable and there are decays as, e.g., $`K^+\pi ^+\pi ^{}\pi ^+`$ (5.59%), but the subsequent decays of the $`\pi ^\pm `$ mesons lead, on the other hand, to neutrinos and $`e^\pm `$. There is also the $`K^0`$ particle, which poses a problem because the principal primary decays of $`K_S^0`$ take place without the emission of neutrinos, but many of the secondary decays emit neutrinos. On the other hand, 2/3 of the primary decays of $`K_L^0`$ emit neutrinos. For comparison 63.6% of $`K^+`$ decay into $`\mu ^++\nu _\mu `$. The decays of the particles in the $`\nu `$-branch follow a mixed rule, either weak or electromagnetic.

To summarize the facts concerning the $`\nu `$-branch of the mesons and baryons. The masses of these particles seem to follow an integer multiple rule if one uses the $`K^\pm `$ meson as reference, however the masses are not integer multiples of the $`\pi ^\pm `$ mesons but share a common factor $`0.86\pm 0.02`$.

We do not want to discuss here the bottom mesons, and the bottom baryon. It is easy to associate the masses of the bottom mesons with integer multiples of the $`\pi ^0`$ meson. For example, $`m(B^0)=1.002939m(\pi ^0)`$ and $`m(B_S^0)=0.994540m(\pi ^0)`$ or $`1.019939m(\pi ^0)`$. The latter numbers show the difficulty in identifying the proper multiple. In this case the difference of the integer multiples is one out of forty or 2.5%, which is too small in order to make a proper identification of the multiple. There are, however, the $`c\overline{c}`$ mesons $`\eta _c`$ and $`\chi _{c0}`$, with $`I,J=0`$, whose masses are $`1.003522m(\pi ^0)`$ and $`1.012025m(\pi ^0)`$, which therefore fall into the range of the masses of the $`\gamma `$-branch considered here, and which are good approximations to integer multiples of $`m(\pi ^0)`$.

## 2 Summary

In spite of differences in charge, spin, strangeness, and charm the masses of the stable mesons and baryons of the $`\gamma `$-branch are, within at most 3.3%, integer multiples of the mass of the $`\pi ^0`$ meson. Correspondingly, the masses of the particles of the $`\nu `$-branch are, after multiplication with a factor $`0.86\pm 0.02`$, integer multiples of the mass of the $`\pi ^\pm `$ mesons. The validity of the integer multiple rule can easily be verified from the Particle Physics Summary using a calculator. The integer multiple rule suggests that the particles are the result of superpositions of modes and higher modes of a wave equation. Such a theory will be presented in a following paper.

The author is grateful to Professor I. Prigogine for his support.
REFERENCE
 R. Barnett et al., Rev. Mod. Phys. 68, 611 (1996).


text:
# Very high rotational frequencies and band termination in 73Br

## Abstract

Rotational bands in 73Br have been investigated up to spins of $`I`$ = 65/2 using the EUROBALL III spectrometer. One of the negative-parity bands displays the highest rotational frequency $`\mathrm{}\omega `$ = 1.85 MeV reported to date in nuclei with $`A25`$. At high frequencies, the experimental $`𝒥^{(2)}`$ dynamic moment of inertia for all bands decrease to very low values, $`𝒥^{(2)}`$ 10 $`\mathrm{}^2`$MeV-1. The bands are described in the configuration-dependent cranked Nilsson-Strutinsky model. The calculations indicate that one of the negative-parity bands is observed up to its terminating single-particle state at spin 63/2. This result establishes the first band termination in the $`A`$ 70 mass region.

23.20.lv, 23.20.En, 21.60.Ev, 27.50.+e

Exploring nuclei at very high excitation energies and angular momentum is of fundamental importance for our understanding of many-body systems. Under such extreme conditions, one of the most interesting quantum phenomena is the termination of rotational bands. This means that a specific configuration manifests itself as a collective rotational band at low spin values, but gradually loses its collectivity with increasing spin and finally terminates at the maximum spin in a fully aligned state of single-particle nature . The origin of this phenomenon lies in the limited angular momentum content of the fixed configuration. Experimentally, terminating bands were first observed in 158Er , then in the $`A110`$ mass region  and recently in several other mass regions . In a terminating band, the nuclear shape gradually traces a path through the triaxial plane, starting as collective (often at near-prolate shape, $`\gamma 0^{}`$) and evolving over many transitions to a non-collective state at oblate ($`\gamma =+60^{}`$), spherical or prolate ($`\gamma =120^{}`$) shape . In the experiment, this has been most clearly demonstrated in the $`A`$ 110 and $`A`$ 60 mass regions .

The A $``$ 70-80 mass region displays a large variety of structural effects. At low spins, there is a competition between prolate and oblate configurations due to the existence of the deformed shell gaps at different particle numbers and deformations . At higher spins, there is a shell gap at near-prolate and near-oblate collective shapes at neutron number 38 . A further interesting observation is that the bands in 81Sr  show features which are generally associated with terminating bands , even though they do not appear to become fully non-collective. It is now an interesting question whether bands can be observed up to termination in the somewhat lighter nuclei in the $`A=70`$ mass region. This is the motivation behind the present study of the $`{}_{35}{}^{}{}_{}{}^{73}`$Br38 nucleus at very high rotational frequencies.

High-spin states in 73Br were populated in the reaction 40Ca(40Ca,$`\alpha 3p`$), using the 185 MeV beam delivered by the XTU Tandem accelerator of the Laboratori Nazionali di Legnaro. The experiment was performed using an enriched (99.96 %) 40Ca target with a thickness of 0.9 mg/cm2. $`\gamma `$-rays were registered with 15 Cluster  and 26 Clover  detectors of the EUROBALL III array. Charged particles were detected with the Italian SIlicon Sphere (ISIS) consisting of 40 Si $`\mathrm{\Delta }EE`$ telescopes . At forward angles, 15 segmented detector units filled with BC501A liquid scintillator were mounted to detect neutrons .

A total number of 2$`\times `$109 $`\gamma \gamma \gamma `$ events were recorded. The $`\alpha 3p`$ exit channel leading to 73Br is predicted to 3.4% of the total cross section, according to PACE calculations . $`\gamma \gamma `$-particle coincidences and $`\gamma \gamma \gamma `$ coincidences were sorted into two-dimensional $`E_\gamma E_\gamma `$ matrices and three-dimensional $`E_\gamma E_\gamma E_\gamma `$ cubes. Examples of doubly-gated coincidence spectra are shown in Fig. 1. These coincidence data were analysed using the Radware package . The resulting level scheme of the 73Br nucleus is presented in Fig. 2. The sequences A, B and C have been known from previous studies  up to the states of spins and parities $`I^\pi `$ = (45/2+), (47/2-) and (49/2-), respectively. In this work, these rotational bands were extended up to states with $`I^\pi `$ = (65/2+), (63/2-) and (65/2-), respectively, at excitation energies $`E`$ $``$ 26 MeV. Moreover, a new sequence D was established, which feeds the 2855 keV, 4020 keV and 5335 keV states of band A.

An analysis of the directional correlations from oriented states (DCO) was performed to assign spins to the newly observed states. The coincidence data were added up for the 35 most backward-angle detectors, located at an average angle of 156 (149, 155, 157, 163) to the beam and the 108 detectors near 90 (72, 81, 99, 107). A 156 versus 90 $`\gamma \gamma `$ matrix was created in coincidence with $`\alpha `$ particles. From this matrix we extracted DCO-ratios defined as:

$`R_{\mathrm{DCO}}^{exp}={\displaystyle \frac{I_{156^{}}^{\gamma _2}(Gate_{90^{}}^{\gamma _1})}{I_{90^{}}^{\gamma _2}(Gate_{156^{}}^{\gamma _1})}}`$ (1)
where $`I_{156^{}}^{\gamma _2}(Gate_{90^{}}^{\gamma _1})`$ denotes the efficiency-corrected intensity of the $`\gamma _2`$ transition observed at 156 when gating on $`\gamma _1`$ at 90. According to the calculations for the DCO-ratios by Krane et al. , values of about 0.5 and 1 are expected for stretched and pure transitions of multipole order 1 and 2, respectively, if the gate is set on an $`E`$2 transition. The DCO-ratios of transitions in 73Br are plotted in Fig. 3. There are two clearly separated groups of transitions around DCO-ratios of 0.6 and 1, which are assigned as dipole and quadrupole transitions, respectively. The DCO-ratio very close to 1 for the 455 keV M1 transition is related to the spin difference $`\mathrm{\Delta }I=0`$ between the initial and final states (see Fig. 2) . On the basis of the DCO-ratios we confirmed the character of all previously known transitions. We furthermore firmly derived an E2 character for the 1651 keV $`\gamma `$-ray in band A, for the 1471 keV, 1637 keV, 1780 keV $`\gamma `$-rays in band B, for the 462 keV and 1593 keV $`\gamma `$-rays in band C, and for the 1210 keV $`\gamma `$-ray depopulating the lowest observed state in band D. Hence, band D has the same signature and parity as band A.

The rotational bands in 73Br display very high $`\gamma `$-ray energies (see Fig. 2). For example the $`\gamma `$-ray energy on the top of sequence C is 3696 keV. This corresponds to a rotational frequency of $`\mathrm{}\omega `$ = $`E_\gamma `$/2 = 1.85 MeV. This is the highest frequency ever observed in a rotational cascade in nuclei with $`A25`$. For comparison, the highest rotational frequencies reported so far are $`\mathrm{}\omega `$ = 1.82 MeV in the 60Zn nucleus  and $`\mathrm{}\omega `$ = 1.4 MeV in the 109Sb nucleus .

A collective parameter which is very sensitive to the changes in the nuclear structure is the dynamic moment of inertia, $`𝒥^{(2)}=(dE_\gamma /dI)^1`$. In Fig. 1 a gradual increase in the $`\gamma `$-ray energy spacings as the $`\gamma `$-ray energies increase within the bands can be clearly seen. This implies a corresponding decrease of the dynamic moments of inertia $`𝒥^{(2)}`$, which are presented in Fig. 4-top. For $`\mathrm{}\omega `$ 1 MeV, the irregularities of $`𝒥^{(2)}`$ are signaling band crossings. For each band there are mainly two irregularities in $`𝒥^{(2)}`$ which could be caused by proton and neutron $`g_{9/2}`$ alignments. In contrast, for frequencies higher than $``$ 1 MeV, the dynamic moments of inertia of the bands converge and decrease to approximately 40 % of the value of a rigid rotor. This smooth down-sloping of the dynamic moment of inertia may indicate that, starting at $`\mathrm{}\omega 1.0`$ MeV, the configurations of bands A and C do not change up to the highest rotational frequency, and that the rotational band is gradually losing its collectivity. For band B a negative spike in $`𝒥^{(2)}`$ occurrs at $`\mathrm{}\omega `$ = 1.28 MeV and is caused by the decrease of the transition energy which indicates a band crossing. This behavior is reminiscent of 158Er where a band terminating at $`I=46^+`$ crosses the more collective yrast band at $`I40`$ . The bottom graph of Fig. 4 shows the kinematical moment of inertia $`𝒥^{(1)}`$ = $`I/\omega `$. The latter stays close to the rigid-body value. For high rotational frequencies the relation $`𝒥^{(1)}𝒥^{(2)}`$ indicates that pairing correlations play no important role.

In order to assign configurations to bands A, B and C we have used the configuration-dependent Cranked Nilsson-Strutinsky (CNS) approach  based on the cranked Nilsson potential. Since we are interested in the high-spin properties, the pairing correlations have been neglected in the calculations. The calculations minimize the total energy of a specific configuration for a given spin with respect to the deformation parameters ($`\epsilon _2,\epsilon _4,\gamma `$). Thus, the total energy and the shape trajectory (the evolution of the minimum of the total energy in the ($`\epsilon _2,\gamma `$) plane as a function of spin) are obtained for each configuration. The configurations of interest can be described by excitations within the $`N=3`$ $`p_{3/2}`$, $`f_{5/2}`$, $`p_{1/2}`$ and the $`N=4`$ $`g_{9/2}`$ orbitals. Thus, there are no holes in the $`f_{7/2}`$ subshell and no particles in the orbitals above the spherical shell gap at 50. In the Ref.  it was shown that at the deformation of $`\epsilon _2`$ = 0.35 the lowest neutron intruder orbital from the $`h_{11/2}`$ subshells comes down and crosses the Fermi surface at $`\mathrm{}\omega `$ = 1.4 MeV. However, the CNS calculations including one neutron in the $`h_{11/2}`$ orbital result in bands which behave very differently from the observed bands.

Furthermore, the highest $`N=3`$ $`p_{1/2}`$ orbital will not become occupied in the low-lying configurations of 73Br; therefore we can omit $`p_{1/2}`$ in the labeling. Note also that all orbitals are treated on the same footing in the cranking calculations, which means that, for example, the polarization of the core is taken care of.

In the following, the configurations will be specified with respect to a $`{}_{28}{}^{}{}_{}{}^{56}`$Ni28 core as having 7 active protons and 10 active neutrons. They will be labeled by the shorthand notation \[$`p_1p_2,n_1n_2`$\], where $`p_1(n_1)`$ stands for the number of protons (neutrons) in the ($`p_{3/2},f_{5/2}`$) orbitals and $`p_2(n_2)`$ stands for the number of protons (neutrons) in $`g_{9/2}`$ orbitals. In addition, the sign of the signature $`\alpha `$ of the last occupied orbital (given as a subscript) is used if the number of occupied orbitals in the specific group is odd.

Considering that the bands A, B and C extend to high spins of $`I=(65/2)`$ or $`(63/2)`$, we will first outline the possible proton and neutron configurations using their maximum spins $`I_{\mathrm{max}}^{p,n}`$ as criteria. The maximum spin is defined from the distribution of particles and holes over the $`j`$-shells at low spin. Including 2 protons in the $`g_{9/2}`$ orbital, there are 5 $`(f_{5/2}p_{3/2})`$ protons, which lead to a maximum proton spin of $`I_{\mathrm{max}}^p=27/2`$ or 29/2 for the proton subsystem depending on signature. The maximum proton spin becomes 33/2 for proton configurations with 3 $`g_{9/2}`$ protons if the last proton occupies the favoured ($`\alpha =+1/2`$) $`g_{9/2}`$ signature. Including 3 neutrons in the $`g_{9/2}`$ orbital, the maximum neutron spin $`I_{\mathrm{max}}^n`$ is 15 or 16 depending on the signature for the 7 $`(f_{5/2}p_{3/2})`$ neutrons. Adding one more neutron to the $`g_{9/2}`$ orbital, the maximum neutron spin is $`I_{\mathrm{max}}^n=18`$. The occupation of additional $`g_{9/2}`$ orbitals adds only marginally to the maximum spin, but costs a lot of energy. Thus, it is reasonable to expect that such configurations will be considerably above the yrast line in the spin range of interest. There are five out of all possible combinations, where the proton and the neutron spins add to a maximum total spin of $`I_{\mathrm{max}}63/2`$. The calculations show that one of these configurations, \[43+,7-3+\], does not build any ‘collective band’ for spin values $`I30`$. Therefore, only four configurations, namely \[43+,64\], \[5+2,64\], \[5-2,64\] and \[43+,7+3+\], are left as possible candidates for the observed bands.

In Fig. 5 the calculated energies relative to a rigid rotor reference $`(EE_{\mathrm{RR}})`$ of the above mentioned configurations are compared with the experimental data. The CNS calculations indicate that these configurations are indeed the lowest-lying ones capable of building angular momentum up to the values observed. Since pairing correlations have been neglected, the calculated energies are expected to be realistic only at high spin of $`I15`$. In the calculations, the configurations are following a parabola-like energy curve. As seen in Fig. 5, the \[43+,64\] configuration has its minimum around spin 61/2, while band A seems to approach the minimum at 65/2. Amongst the considered configurations, the \[5+2,64\] configuration is calculated to be lowest up to spin $`I=57/2`$, which reproduces the experimental situation with band C. Moreover, the minimum in $`(EE_{\mathrm{RR}})`$ occurs at similar spin values, 57/2 in band C and at 53/2 in the \[5+2,64\] configuration. Based on this comparison of theoretical and experimental energies we assign the \[43+,64\] and \[5+2,64\] configurations to bands A and C, respectively.

Band B is observed up to $`I`$ = (63/2). The calculations suggest that the \[5-2,64\] configuration can be assigned to this band at low and medium spin. It is the signature partner of the \[5+2,64\] configuration assigned to band C. These configurations reproduce well the slope of experimental $`(EE_{\mathrm{RR}})`$ curves for bands B and C, but underestimate the signature splitting between them. The \[5-2,64\] configuration is crossed at spin 57/2 by the \[43+,7+3+\] configuration (see Fig. 5). The predicted crossing is indeed observed in band B at spin (55/2-) (Fig. 2). Thus, the latter configuration can be related to band B above the band crossing. In the calculations, the band built on the \[43+,7+3+\] configuration terminates at the maximum spin of the particle configuration, i.e. at 63/2. This can be seen in the shape trajectories, which are presented in Fig. 6. Whereas the trajectories related to bands A and C include collective near-prolate deformations over the whole spin range, the configuration assigned to band B after the band crossing at 55/2 (empty triangles) undergoes a shape change from a collective $`\gamma +30^{}`$ shape to a non-collective oblate $`\gamma =+60^{}`$ shape between spins 55/2 and 63/2. Thus, the band built on this configuration terminates at the maximum spin $`I_{\mathrm{max}}=63/2`$. Since this coincides with the maximum spin observed in band B, we have observed this band up to its termination. Our interpretation of band B requires a relatively strong interaction between two configurations which differ in their occupation of the $`j`$-shells for both protons and neutrons. This might appear unlikely but one could also note that a high-spin crossing in a terminating band in 108Sn has been interpreted  as built from configurations which differ in an analogous manner.

In band A a branching at spin $`I`$ = (53/2) is experimentally seen (see Fig. 2). The configuration assigned to this band shows a shape change from $`\gamma 15^{}`$ to $`\gamma +5^{}`$ (see Fig. 6) between $`I`$ = 53/2 and 57/2. This suggests that in each minimum, there is a smooth configuration and the calculated yrast configuration jumps from one minimum to the other with increasing spin. Thus, the two states at (53/2) might belong to these different minima. A similar branching is also observed for the band C, but appears even more difficult to describe in the calculations even though the irregularities in the shape trajectories (Fig. 6) suggest the possibility of competitions between different minima in all configurations shown in Figs. 5 and 6. However, these branchings remain an interesting experimental result and a challenge to theory.

In summary, we observed in the 73Br nucleus the highest rotational frequency in a cascade in nuclei with $`A25`$. Out of the four observed rotational bands could be followed up to its termination. Moreover, we give arguments on the particle structure of this band. According to the calculations the other two high-spin bands are not terminating; instead they stay collective beyond the maximum spin defined from the distribution of particles and holes over the $`j`$-shells at low spin. These results establish the phenomenon of band termination in the $`A70`$ mass region for the first time. The predicted decrease in the quadrupole moment along the terminating band should be observable via Doppler shift lifetime measurements. Further studies will be important in order to obtain greater insight into the systematics of the physical observables in connection with band termination in this mass region.

This work was supported by the German Ministry of Education and Research under contracts 06 DR 827, 06 OK 862, 06 GOE 851, by the Swedish Natural Science Research Council, by the UK EPSRC, and by the European Union within the TMR project. A.V. Afanasjev acknowledges the support by the Alexander von Humboldt Foundation.


text:
# An eigenfunction method for particle acceleration at ultra-relativistic shocks

## The method

We study a stationary shock front in the $`xy`$plane. The accelerated particles are assumed to be test-particles without influence on the dynamics of the plasma or the jump conditions at the shock-front. The plasma flows along the $`z`$-axis, with constant velocities $`u_{}`$ in the upstream ($`z<0`$) region and $`u_+`$ downstream ($`z>0`$), the velocities are related by the Rankine-Hugoniot jump conditions.

Test-particles are injected into the acceleration process and their interaction with the plasma flow is assumed to give rise to diffusion in the angle $`\mathrm{cos}^1\mu `$ between a particle’s velocity and the shock normal. In the frame of the shock front this leads to a stationary transport equation valid for the local plasma rest frame and given in mixed coordinates as aguthmann:kirkschneider87

$$\mathrm{\Gamma }(u+\mu )\frac{f}{z}=\frac{}{\mu }D_{\mu \mu }(1\mu ^2)\frac{f}{\mu }$$
(1)
where the plasma speed $`u`$ is measured in units of the speed of light, $`\mathrm{\Gamma }=\left(1u^2\right)^{1/2}`$ is the Lorentz-factor, $`f(p,\mu ,z)`$ is the (Lorentz invariant) phase-space density as a function of the particle momentum $`p`$, direction $`\mu `$ and position. $`p`$ and $`\mu `$ are measured in the local rest frame of the plasma, whereas $`z`$ is measured in the rest frame of the shock front.

Equation (1) is solved using the separation Ansatz aguthmann:kirkschneider87

$$f(p,u,\mu ,x)=\underset{i=\mathrm{}}{\overset{+\mathrm{}}{}}g_i(p)Q_i(\mu ,u)\mathrm{exp}\left(\mathrm{\Lambda }_iz/\mathrm{\Gamma }\right),$$
(2)
valid in each half-plane with $`\mathrm{\Lambda }_i`$ and $`Q_i`$ the eigenvalues and eigenfunctions of the equation

$$\left\{\frac{}{\mu }\left[D_{\mu \mu }\frac{}{\mu }\right]\mathrm{\Lambda }_i(u+\mu )\right\}Q_i(\mu ,u)=0$$
(3)
The momentum distribution of particles with energy far above the injection energy range – those in which we are interested – takes the shape of a power-law $`g_i(p)p^s`$ with a power-law index $`s`$, since there is no preferred momentum scale in this range.

Matching the expansion (2) across the shock front according to Liouville’s Theorem and imposing physically realistic boundary conditions up and downstream leads to a nonlinear algebraic equation for the power law index $`s`$.

In aguthmann:kirkschneider87  and aguthmann:heavensdrury88  only the eigenfunctions with $`i<0`$ were used and the method was applied to mildly relativistic shock speeds ($`\mathrm{\Gamma }_{}5`$). Here, we use the eigenfunctions with $`i>0`$ and calculate them directly with a numerical scheme. In the limit $`u_{}1`$ an analytic expression is available aguthmann:kirkschneider89 . Four eigenfunctions ($`i=1,3,5,7`$) are shown in Fig. 1A as functions of the cosine $`\mu _\mathrm{s}=(\mu +u)/(1+\mu u)`$ of the angle between the particle direction and the shock normal, measured in the shock rest frame. For $`i>1`$ they are oscillatory for $`1<\mu _\mathrm{s}<0`$ and for all $`i>0`$ fall off monotonically in the range $`0<\mu _\mathrm{s}<1`$.

## Results

The index $`s`$ of the momentum spectra of the accelerated particles in different cases are shown in Fig. 1B. The jump conditions investigated are those for a relativistic gas both up and downstream: $`u_{}u_+=1/3`$ and for a strong shock in a medium with adiabatic index $`4/3`$ aguthmann:kirkduffy99 .

Also we investigate two different scattering operators, $`D_{\mu \mu 1}=1\mu ^2`$ (isotropic small/angle scattering) and $`D_{\mu \mu 2}=(1\mu ^2)\times (\mu ^2+0.01)^{1/3}`$ corresponding to scattering in weak Kolmogorov turbulence, together with a rough prescription for avoiding the lack of scattering at $`\mu =0`$ aguthmann:heavensdrury88 . For high upstream Lorentz-factors the power-law index settles at a value around $`4.23`$ for all equations of state, which is reproduced in the limiting case $`u_{}1`$. The scattering operator has only a minor effect.

## Summary

These results are in agreement with the asymptotic Monte-Carlo results of Gallant et al. aguthmann:gallant  and those of Bednarz & Ostrowski aguthmann:bednarz  for $`\mathrm{\Gamma }_{}200`$. Anisotropic scattering, which has not been treated by Monte-Carlo simulations, leads to a slight steeping in the power-law spectrum, because fewer particles are able to cross the region $`\mu 0`$ and return to the shock. From observations of GRB afterglows, Galama et al. aguthmann:galama  and Waxman aguthmann:waxmann  have found synchrotron spectral indices corresponding to $`s4.25`$, implying that the particles could indeed have been accelerated by the first order Fermi mechanism operating at an ultrarelativistic shock front.

###

This work was supported by the European Commission under the TMR programme, contract number ERBFMRX-CT98-0168


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# Vibrational States of Glassy and Crystalline Orthoterphenyl

## 1 Introduction

Orthoterphenyl (OTP) has been studied for more than fourty years as prototype of a non-associative, non-polar molecular glass former AnUb55 . Early studies concentrated on viscosity AnUb55 ; LaUb58 ; GrTu67 ; LaUh72 ; CuLU73 ; ScKB98  and $`\alpha `$-relaxation WiHa71 ; WiHa72 ; Arr75 ; VaFl80 ; FyWL81 ; DiNa88 ; MeFi88 ; FiBH89  as direct manifestations of the frequency-dependent glass transition, or on slow $`\beta `$ relaxation JoGo70a ; JoGo70b ; WuNa92 .

In the past decade, a new frame has been set by mode-coupling theory Got91 ; GoSj95 ; Cum99  which describes the onset of structural relaxation on microscopic time scales. Consequently, the fast dynamics of OTP has been studied by incoherent BaFK89b ; PeBF91 ; KiBD92 ; WuKB93 ; ToSW98a  and coherent BaFL95 ; ToSW97b ; ToWS98b  inelastic neutron scattering as well as by depolarised light scattering StPG94 ; SoSR95 ; CuLD97b  and is found to be in good accord with asymptotic results of theory.

Closed formulations of mode-coupling theory exist only for very simple systems consisting of spherical particles BeGS84  or mixtures thereof BoTh87 , and the generalisation to dipolar molecules requires already intimidating formal efforts FrFG97c ; ScSc97 . Intramolecular vibrations have not yet been explicitely considered, and therefore the fit of mode-coupling asymptotes to complex systems like OTP remains heuristic. Worse: theoretical studies of a hard-spheres system FrFG97b ; FuGM98  have shown that the full asymptotic behaviour is only reached when the relaxational time scale is separated by several orders of magnitude from the microscopic dynamics, whereas experimental studies are restricted to at best three decades in time or frequency. On this background the present communication shall supplement our neutron scattering studies of relaxational dynamics in OTP BaFK89b ; PeBF91 ; KiBD92 ; WuKB93 ; ToSW98a ; BaFL95 ; ToSW97b ; ToWS98b  by an explicit investigation of vibrational states.

As other glasses, OTP possesses more low-frequency modes than expected from the Debye model. This excess, for obscure reasons named “boson-peak”, is usually taken as a characteristic feature of disordered systems. To substantiate this interpretation, glasses and crystals must be compared systematically, which so far has been done for very few systems Lea69 ; GoLa81 ; Gom81 ; CrBA94 ; BeCM94 ; BeCA96 ; MeWP96a ; DoHH97 ; CuBF98 ; TaRV98 ; BeCC98 .

OTP crystallises easily into a polycrystalline powder. Some effort is needed to prevent it from crystallisation when cooling below the melting point Tm=329 K. It forms a stable glassy structure when it is supercooled below the caloric glass transition temperature Tg=243 K. One particular advantage is that large single crystal specimens of several cm3 can be grown. So we are able to compare scattering from a single crystal, from powder-like polycrystal, and from the glass.

The paper is organised as follows: The analysis of single crystal dispersion relations in Sec. 2 enables us to fix the frequency range of acoustic modes in the ordered state. The vibrational density of states and the derived thermodynamic quantities of the glass and the polycrystal are compared with each other in Sec. 3. The temperature effect on the frequency distributions in the crystal and the glass is presented in Sec. 4.

## 2 Single Crystal: Phonon Dispersions

### 2.1 Structural Information

The OTP molecule (1,2-diphenyl-benzene: C18H14) consists of a central benzene ring and two lateral phenyl rings in ortho position.

The crystal structure belongs to the orthorhombic space group $`P2_12_12_1`$ with four molecules per unit cell and lattice parameters $`a=18.583`$ Å, $`b=6.024`$ Å, $`c=11.728`$ Å at room temperature BrLe79 ; AiMO78 . A sketch of the structure is given in Fig. 1 of Ref. BrLe79 .

For steric reasons, the lateral phenyl rings are necessarily rotated out of plane. In addition, the overcrowding in the molecule leads to significant bond-angle and out-of-plane distortions of the phenyl-phenyl bonds. Such structural irregularities may explain why OTP can be undercooled far easier than $`m`$\- or $`p`$-terphenyl AnUb55 .

In the crystal, the angles for the out-of-plane rotation of the lateral phenyl rings are $`\varphi _143^{}`$ and $`\varphi _262^{}`$ BrLe79 ; AiMO78 . For isolated molecules, an old electron diffraction study had suggested $`\varphi _1=\varphi _2=90^{}`$, but newer experiments and calculations agree that in the gas or liquid phase $`40^{}\varphi _1,\varphi _265^{}`$ BaPo85 .

### 2.2 Triple-Axis Experiment

For coherent neutron scattering, perdeuterated OTP (C18D14, $`>`$ 99 % deuteration) was used. Single crystals of high quality and considerable size (several cm3) were grown out of hot methanol solution either by very slow cooling or by evaporation over several months. They grew preferentially along the shortest axis $`b`$.

The phonon dispersion measurements were carried out on a specimen of about $`1\times 1\times 2`$ cm3 for temperatures between 100 and 310 K. The experiments were performed on the cold triple-axis spectrometer IN12 at the Institut Laue Langevin (ILL), mostly with constant final wave vector $`k_f=1.55`$ Å-1.

The lattice parameters as measured on IN12 at room temperature $`a=18.53`$ Å, $`b=6.02`$ Å, $`c=11.73`$ Å are in good agreement with the literature results from neutron BrLe79  and X-ray diffraction AiMO78 . On cooling to 100 K, $`a`$ and $`c`$ change only by a few ppm, whereas $`b`$ contracts by about 3 %.

### 2.3 Acoustic Phonons

In Fig. 1 we present the measured phonon dispersion of crystalline OTP at 200 K along the three main symmetry directions , , and . Within the available beam time not all acoustic modes could be investigated. Some optic phonons were detected as well, but not studied in detail; as an example, the lowest optic branch in  direction is included in Fig. 1.

Due to the crystal symmetry modes of longitudinal and transverse character are pairwise degenerated at the Brillouin zone boundary. A first interesting point is that purely acoustic modes are confined to a rather small frequency range: crossing with optic-like branches occurs already at about 0.6 THz.

Lattice dynamics calculations CrBA94  agree qualitatively with the measured acoustic dispersions. For instance, the crossing of the longitudinal acoustic mode in  direction with optic branches is predicted correctly. Quantitatively, the measured acoustic dispersions are considerably steeper than calculated. The sound velocities, determined from the initial slopes, are summarised in Table 1; they lie 20–60% above the calculated values. In all lattice directions, longitudinal sound modes are almost twice as fast as transverse modes.

The single crystal data may also be compared with sound velocities in the glass. Results from Brillouin scattering are summarised in Table 2. Taking the simple arithmetic average over the three crystal axes, the mean longitudinal and transverse sound velocities $`v_{\mathrm{L},\mathrm{T}}`$ exceed those of the glass by about 20 % and 27 %, respectively.

## 3 Glass and Polycrystal: Density of Vibrational States

### 3.1 Density of States and Neutron Scattering

In the absence of crystalline order, it is no longer possible to measure selected phonon modes with well-defined polarisation and propagation vector. For polycrystalline or amorphous samples, the distribution of vibrational modes can be conveyed only in form of a spectral density of states (DOS).

In principle, the DOS can be measured in absolute units by incoherent neutron scattering. However, as soon as one goes beyond the simplest textbook example of a harmonic, monoatomic, polycrystalline solid with a simple (ideally cubic) lattice, several difficulties arise and the very concept of a DOS becomes problematic.

In a molecular solid, different atoms $`j`$ participate in given vibrational modes $`r`$ with different amplitudes $`𝐞_j^r`$. Therefore, atoms in non-equivalent positions have different vibrational densities of states $`g_j(\nu )`$. In neutron scattering, these $`g_j(\nu )`$ are weighted with the scattering cross sections $`\sigma _j`$. In the case of protonated OTP, we see almost only incoherent scattering from hydrogen. Worse, in the scattering law $`S(q,\nu )`$ the $`g_j(\nu )`$ of non-equivalent hydrogen atoms are weighted with a prefactor $`|𝐞_j^r|^2`$ and a Debye-Waller factor that depends also on $`j`$.

Only for low-frequency, long-wavelength vibrations the molecules (or some structural subunits) move as rigid bodies, the $`g_j(\nu )=g(\nu )`$ become the same for all $`j`$, and the $`𝐞_j^r`$ become independent of $`r`$ WuKB93 ; CaPe75a . In this limit, the determination of $`g(\nu )`$ from a neutron scattering law remains meaningful and feasible.

### 3.2 Experiments and Data Reduction

Vibrational spectra from glassy OTP between 160 and 245 K have been analysed previously WuKB93 . For the present comparison, we measured incoherent scattering from the glass at 100 K, and from the polycrystalline powder at 100, 200, and 300 K on the time-of-flight spectrometer IN6 at the ILL with an incident wavelength of 5.1 Å. If not stated otherwise, we refer in the following to the 100 K data. In these experiments, protonated OTP was used. OTP of $`>`$ 99 % purity was bought from Aldrich and further purified by repeated vacuum distillation.

The raw data were converted into $`S(2\theta ,\nu )`$ and the container scattering subtracted. Without interpolating to constant wavenumbers $`Q`$, we calculated the DOS directly from $`S(2\theta ,\nu )`$, preferentially using data from large scattering angles $`2\theta `$. Multi-phonon contributions were calculated by repeatedly convoluting $`g(\nu )`$ with itself and subtracting it from $`S(2\theta ,\nu )`$ in an iterative procedure, as described in detail in WuKB93 .

The so-obtained DOS shows a pronounced gap above $`\nu _\mathrm{g}5`$ THz. Comparing our results with model calculations Bus82 , we assign all vibrations below $`\nu _\mathrm{g}`$ to the 16 degrees of freedom needed to describe the crystal structure. For 16 low-lying modes in a molecule with 32 atoms, we expect an integrated DOS

$$_0^{\nu _\mathrm{g}}d\nu g(\nu )=\frac{16}{32}=0.5.$$
(1)
This condition is used to readjust the absolute scale of $`g(\nu )`$. In the Appendix, we argue that the difference between measured and re-normalised $`g(\nu )`$ is mainly an effect of multiple scattering.

### 3.3 Density of States in Orhoterphenyl

Fig. 2 shows the DOS of glassy and crystalline OTP at 100 K. Rather broad distributions are found for both phases. In the glass a first shoulder around 1.5 THz is followed by a second at 3.5 THz in accordance with results from Raman studies CrBA94 ; KiVP99 . As expected, the crystal DOS is more structured, in particular in the low energy region. Distinct peaks at 0.6, 0.8, 1.1 and 1.5 THz become apparent. They are due to strong contributions from zone-boundary modes, as can be seen from Fig. 1. Compared to the glass, significant density is missing in the low energy region and in the range from 1.5 to 3 THz, and reappears at higher frequencies around 3.5 THz.

In order to show the low energy modes on enhanced scale, we plot in Fig. 3 $`g(\nu )/\nu ^2`$ which in the one-phonon approximation is proportional to $`S(Q,\nu )`$ itself. In this representation, the excess of the glass over the crystal becomes evident. A well defined frequency peak appears around 0.35 THz which is downshifted with respect to the first peak of the crystal at 0.6 THz and superposed to a long tail which is similar for glass and crystal. Note that the maximum of the boson peak at 0.35 THz is located below the lowest acoustic zone-boundary phonons in the crystal.

The DOS of the polycrystalline sample is in accord with the measured dispersion of the single crystal: A small shoulder at 0.4 THz can be attributed to the transverse acoustic zone-boundary phonons in $`[100]`$ direction, and the main peak at 0.6 THz corresponds to the transverse acoustic zone-boundary phonons in the other two lattice directions. The peak at 0.8 THz reflects the longitudinal acoustic zone-boundary phonon in $`[001]`$ direction and the transverse optic in $`[010]`$ direction.

We performed additional coherent scattering experiments on a deuterated sample, which show that the frequency of the boson peak maximum has no dispersion for wave numbers in the range 0.8 to 2 Å-1. Its intensity is modulated in phase with the static structure factor, in accordance with observations in other glasses MeWP96a ; BuWR96b .

### 3.4 Mean Square Displacement

Another dynamic observable which can be obtained from neutron scattering is the atomic mean square displacement $`r^2(T)`$. Roughly speaking, $`r^2(T)^{3/2}`$ measures the volume to which an atom remains confined in the limit $`t\mathrm{}`$.

For a large class of model situations (harmonic solid, Markovian diffusion, …) it can be obtained directly from the Gaussian $`Q`$ dependence of the elastic scattering intensity

$$S(Q,\nu =0)=\mathrm{exp}(Q^2r(T)^2).$$
(2)
For a harmonic solid,

$$r(T)^2=\frac{\mathrm{}^2}{6Mk_\mathrm{B}T}_0^{\mathrm{}}d\nu \frac{g(\nu )}{\beta }\mathrm{coth}(\frac{\beta }{2})$$
(3)
with $`\beta =h\nu /k_\mathrm{B}T`$ crosses over from zero-point oscillations $`r^2(0)`$ to a linear regime $`r^2(T)T`$ x43 . In any real experiment, which integrates over the elastic line with a resolution $`\mathrm{\Delta }\nu `$, one measures actually atomic displacements within finite times $`t_\mathrm{\Delta }2\pi /\mathrm{\Delta }\nu `$.

Fig. 4 shows mean square displacements of OTP, determined according to (2) from elastic back-scattering (fixed window scans on IN13, with $`t_\mathrm{\Delta }100200`$psec) and from Fourier-deconvoluted time-of-flight spectra (taking the plateau $`S(Q,t_\mathrm{\Delta })`$ with $`t_\mathrm{\Delta }510`$psec from IN6 data that were Fourier transformed and divided through the Fourier transform of the measured resolution function). For the glassy sample, a direct comparison can be made and shows good agreement between IN6 and IN13. In the polycrystalline sample, the displacement is for all temperatures smaller than in the glass.

The lines in Fig. 4 are calculated through (3) from the DOS at 100 K. For low temperatures, the $`r^2(T)`$ are in full accord with the values determined through (2). This comparison can be seen as a cross-check between the analysis of elastic and inelastic neutron scattering data.

Equation (3) gives not only the absolute value of $`r^2(T)`$, but enables us also to read off which modes contribute most to the atomic displacement. To this end, we restrict the integration (3) to modes with $`0<\nu <\nu ^{}`$. The inset in Fig. 4 shows the relative value $`r^2(\nu ^{};T)^{1/2}/r^2(\nu ;T)^{1/2}`$ for $`T=100`$K as function of $`\nu ^{}`$. Modes below 0.6 THz in the crystal, or 0.4 THz in the glass contribute about 55% to the total displacement; 90% are reached only at about 2 THz. This means that the modes which are responsible for the mean square displacement and the Debye-Waller factor are not rigid body motions alone, but contain a significant contribution from intramolecular degrees of freedom.

### 3.5 Debye-Limit and Sound Velocity

Assuming Debye behaviour at very low frequencies $`g(\nu )=9\nu ^2/\nu _D^3`$, we can compare the neutron DOS with the Debye frequency calculated from experimental density and sound velocities:

$$(2\pi \nu _\mathrm{D})^3=\frac{V}{18\pi ^2N}\left(\frac{1}{v_\mathrm{L}^3}+\frac{2}{v_\mathrm{T}^3}\right)$$
(4)
where $`N`$ is the number of molecules in volume $`V`$. For the sound velocities of the crystal, we take the average $`v^3^{1/3}`$ over the three lattice directions of our triple-axis experiment at 200 K. For the glass, we take literature data HiWa81  from Brillouin scattering at 220 K. The so-obtained $`9/\nu _D^3`$ are indicated by arrows in Fig. 3.

In both cases, but in particular for the glass, the neutron DOS extrapolates to a far higher Debye level than expected from the sound velocities. Part of the large discrepancy may be due to inaccurate estimates for the sound velocity (see tables) (for instance, the velocities from Brillouin scattering are based on a temperature extrapolation of the refraction index) or due to the circumstance of a broad tail of the resolution of IN6 and a boson peak of OTP which is located at exceptionally low frequency. But for the main part, we must conclude that our neutron scattering experiment on the glass simply does not reach the Debye regime.

In many other glass forming systems, similar discrepancies between DOS and sound velocities are established as well BuPK88 ; GiRB93 ; WiBD98 , although in some substances a better accord is found ZoAC95 ; WuPC95 . Anyway, our data leave the possibility open that the low-frequency spectrum of the glass and the crystal contain non-harmonic, relaxational contributions, as have been found recently by light scattering MoFM99 ; MoCL99  or additional glassy excitation.

### 3.6 Heat Capacity

For a harmonic solid, the heat capacity is given by the integral

$$c_p(T)c_V(T)=N_{\mathrm{at}}R_0^{\mathrm{}}d\nu g(\nu )\frac{(\beta /2)^2}{\mathrm{sinh}^2(\beta /2)}.$$
(5)
With a Debye DOS, this yields the well-known $`c_pT^3`$. Therefore, in Fig. 5 experimental data ChBe72  for the specific heat of glassy and polycrystalline OTP are plotted as $`c_p/T^3`$. In this representation, a boson peak at 0.35 THz is expected to lead to a maximum at about 4 K.

The lines which are calculated through (5) from the neutron DOS agree for both glass and crystal in absolute units and over a broad temperature range with the measured data. Similar accord has been reported for a number of other systems CrBA94 ; BeCA96 ; TaRV98 ; WuPC95 ; BuPN86 .

At higher temperatures, the heat capacities of crystalline and glassy OTP differ only little (e.g. at 200 K: $`c_p^{\mathrm{cryst}}=182.8`$ J mol-1 K-1 and $`c_p^{\mathrm{glass}}=186.1`$ J mol-1 K-1 ChBe72 ). Towards high frequencies, the DOS becomes less sensitive to the presence or absence of crystalline order (as suggested by the representation Fig. 3 for $`\nu 1`$THz), and remaining differences (clearly visible in Fig. 2) are largely averaged out by the integral (5).

## 4 Thermal effects

Figures 6–8 show the temperature evolution of vibrations in single crystal, polycrystal and glass.

In the single crystal, some phonons become softer on heating, others become stiffer, depending on their direction, as exemplified in Fig. 6. Broadening could not be observed because the linewidth remained always limited by the resolution of the spectrometer.

The temperature dependence of the different phonons is in accord with results from Raman scattering on a polycrystal CrBA94  where substantial positive and negative frequency shifts and broadening were observed already above 70 K, indicating the presence of anharmonicities even at these low temperatures. The opposite trends in the temperature evolution of different modes ensure that the overall anharmonic effects are small, although individual modes are clearly anharmonic.

Through exceptionally large negative Grüneisen parameters the softening of certain phonons may be related to anisotropic thermal expansion. Negative expansion coefficient have indeed been found in crystalline OTP at much lower temperatures ($`T<30`$ K) RaVB95 .

In the frequency distributions of the polycrystal systematic temperature effects are detected as well (Fig. 7a). In Fig. 7b we find a slight increase in the Debye limit ($`\nu 0`$) of $`g(\nu )/\nu ^2`$, which may be explained by regular thermal expansion and softening — the kind of effects which can be accomodated in the harmonic theory of solids by admitting a temperature-dependent, “quasiharmonic” density of states $`g(\nu ;T)`$.

In the glass the temperature effects are weak; only around 2 THz a systematic change in $`g(\nu )`$ may be recognised in Fig. 8a. In the low-frequency DOS, shown as $`g(\nu )/\nu ^2`$ in Fig. 8b, the temperature variation is stronger than in the polycrystalline counterpart. The increase starts at about 160 K, far below the glass transition.

The same anharmonicity of low-lying modes is also responsible for the temperature dependence of the mean square displacement. Fig. 4 shows that $`r^2(T)`$ starts to increase faster than expected from (3) already at about 140 K. These anharmonic contributions to $`r^2(T)`$ amount to about 20% at 200 K for both phases, the crystal being slightly smaller. Note, that around 140 K deviations from the proportionality $`\mathrm{ln}S(Q,\nu =0)T`$ are also observed in coherent elastic scans on the BS instrument IN16. The additional increase of $`r^2(T)`$ above about 240 K has been consistently interpreted as the onset of fast $`\beta `$ relaxation PeBF91 . At higher temperatures, in the presence of quasielastic scattering from relaxational modes, the multi-phonon cross-section becomes ill-defined, and the iterative determination of a DOS is no longer possible.

With a temperature-dependent DOS, the heat capacity can be expressed as HuAl75

$$c_p(T)=N_{\mathrm{at}}R_0^{\mathrm{}}d\nu g(\nu ;T)\frac{(\beta /2)^2}{\mathrm{sinh}^2(\beta /2)}\left[1\left(\frac{\mathrm{ln}\nu }{\mathrm{ln}T}\right)_p\right]$$
(6)
where the second term arises explicitely from the shift of phonon modes. The temperature derivative of the logarithmic moment

$$\mathrm{ln}\nu =_0^{\mathrm{}}d\nu g(\nu )\mathrm{ln}\nu $$
(7)
can then be taken as a direct measure for the degree of anharmonicity. For Fig. 9, the integral (7) has been evaluated with an upper integration limit $`\nu _\mathrm{g}=5`$THz. From the plot of $`\mathrm{ln}\nu `$ versus $`\mathrm{ln}T`$ we estimate slopes $`\mathrm{ln}\nu /\mathrm{ln}T`$ of $`0.019`$ for the polycrystal and $`0.012`$ for the glass. The stronger anharmonicity of the crystal can be traced back to the softening of high-frequency modes.

## 5 Discussion

Our incoherent scattering experiments reconfirm that it is possible to determine a meaningful DOS for a molecular system like OTP. Cross-checks versus $`r^2(T)`$ and $`c_p(T)`$ show excellent accord if only the absolute scale of $`g(\nu )`$ is corrected for multiple-scattering effects.

By coherent scattering on a single crystal low-lying phonon branches could be resolved. The low-frequency peaks in the DOS of the polycrystal can be assigned to zone-boundary modes. Optic phonons and hybridisation are found at rather low frequencies. The excess of $`g(\nu )`$ of the glass over the crystal is restricted to frequencies below about 0.5 THz, the region where the crystal possesses mainly acoustic modes. Towards higher frequency, the DOS is less structured in the glass than in the polycrystal, but the overall spectral distribution is rather similar.

The main result of this communication concerns the strong thermal effects as they were manifested earlier close to the glass transition. With increasing temperature, the glass shows less anharmonicity than the polycrystal. However, this may be partly due to a cancellation of opposite effects. An example is provided by different phonon branches of the single crystal for which positive, negative, and nearly vanishing temperature coefficients are found. In both, crystal and glass the anharmonic contributions to the mean square displacement occur above $`150`$ K. However, the anomalous increase in $`r^2(T)`$ is much stronger in the glass, leading to the known glass transition anomalies.

Finally, concering our previous analysis of quasielastic scattering in the supercooled liquid OTP we can state: Hybridisation and coupling between inter- and intramolecular modes plays an important role for frequencies higher than 0.6 THz. As a consequence, the quasielastic scattering, which is confined to below 0.25 THz, is clearly dominated by rigid-body motions and the analysis in terms relaxations in the framework of the mode coupling theory remains reasonable.

## Acknowledgements

We thank A. Doerk (Institut für Physikalische Chemie, Mainz) for help in purifying several samples. Financial support by BMBF under project numbers 03fu4dor5 and 03pe4tum9 is gratefully acknowledged.

## Appendix

The determination of a density of states in absolute units is complicated by the inevitable presence of multiple scattering. In the inelastic spectrum of a glass, most multiple-scattering intensity comes from elastic-inelastic scattering histories Sea75 . This contribution is nearly isotropic, tends to smear out the characteristic $`Q`$ dependence of the phonon scattering, and dominates at small angles where the single-scattering signal is expected to vanish as $`Q^2`$.

In our previous analysis of incoherent scattering from glassy OTP we performed a Monte-Carlo simulation for an ideal harmonic system with given $`g(\nu )`$ WuKB93 . Here, we simply expand the scattering function $`S(Q,\nu )=A(\nu )+Q^2B(\nu )+\mathrm{}`$ which enables us to estimate the multiple scattering $`A(\nu )`$ by $`Q^20`$ extrapolation from the $`S(2\theta (Q,\nu ),\nu )`$ spectra. Results are shown in Fig. 10a. For 200 K, good accord with the Monte-Carlo simulation is found, and measured spectra can be corrected by simply subtracting $`A(\nu )`$. The interplay between multi-phonon scattering and multiple scattering limits this procedure to frequencies $`\nu 3`$ THz.

In the low-frequency region, the subtraction of $`A(\nu )`$ leads to almost the same DOS as the ad hoc normalisation of Sect. 3.2. This confirms our assignment of the 16 modes below the gap, and it shows at the same time that multiple scattering is indeed the main obstacle to a quantitative determination of a generalised density of vibrational states.

Figure captions:
Figure 1:
Phonon dispersion relations of crystalline orthoterphenyl as measured on the triple axis spectrometer IN12 at 200 K. The wave vectors are given in reciprocal lattice units.

Figure 2:
Renormalized density of vibrational states of glassy ($`\mathrm{}`$) and crystalline OTP ($`\mathrm{}`$) at 100 K obtained from IN6.

Figure 3:
Density of vibrational states of glassy ($`\mathrm{}`$) and crystalline OTP ($`\mathrm{}`$) at 200 K. To emphasise the excess density of states of the glass over the crystal $`g(\nu )/\nu ^2`$ is shown. The arrows mark the Debye limit $`\nu 0`$ calculated from sound velocities and densities (at 220 K for the glass and at 200 K for the crystal).

Figure 4:
Mean square displacement $`r^2(T)`$ of glassy OTP from elastic back-scattering (IN13, $`\mathrm{}`$) and from time-of-flight spectra (IN6, plateau value of $`S(q,t)`$, $`\mathrm{}`$). For comparison, IN6 data of polycrystalline OTP are also shown ($`\mathrm{}`$). The lines are calculated from the densities of states at 100 K of the glass (dashed) and the polycrystal (solid line). The inset shows the relative value of $`d=r^2^{1/2}`$ at 100 K for the crystal and the glass when the integral (3) is restricted to modes with $`0<\nu <\nu ^{}`$.

Figure 5:
Experimental heat capacity capacities $`c_p/T^3`$ of glassy and crystalline OTP ChBe72 , compared to $`c_p/T^3`$ calculated from the density of vibrational states $`g(\nu )`$ at 100 K.

Figure 6:
Examples for the temperature dependence of phonons along different directions. Hardening (left, note the negative energy scale), softening (middle) Our data leave the possibility open that the low-frequency spectrum of the glass and the crystal contains non-harmonic, relaxational contributions. and nearly no temperature variation (right) is observed with increasing temperature. The intensities are Bose corrected. The remaining differences are due to the use of different set-ups (collimation).

Figure 7:
(a) Vibrational density of states of polycrystalline OTP for three different temperatures. Note the significant temperature dependence of the DOS for all frequencies. — (b) To emphasise the temperature evolution at small energies, the same data are plotted as $`g(\nu )/\nu ^2`$. The temperature dependence of the low-frequency modes becomes apparent.

Figure 8:
(a) Temperature dependence of the vibrational density of states of glassy OTP. — (b) The low frequency region of (a) plotted as $`g(\nu )/\nu ^2`$. Above 160 K the density of low-frequency modes increases strongly.

Figure 9:
The logarithmic moment $`\mathrm{ln}\nu `$ versus $`\mathrm{ln}T`$ of the density of states of glassy and crystalline OTP. From the straight line, one obtains the slope $`\mathrm{ln}\nu /\mathrm{ln}T`$ which is a measure for the anharmonicity.

Figure 10:
(a) Comparison of the experimental data at two scattering angles with the multiple scattering contribution obtained by an $`Q^20`$ extrapolation. The MS nearly completely dominates the scattering signal at small angles. — (b) Comparison of the density of states obtained from the MS-corrected spectra with the ad hoc normalized DOS.