# Numerical studies of the vibrational isocoordinate rule in chalcogenide glasses

## I Introduction

Establishing the microscopic properties of disordered materials based on macroscopic probes is a difficult endeavor: the charateristic isotropy of these materials limits measurements to mostly scalar, orientation-averaged properties, reducing significantly the amount of information accessible compared with, for example, what is available in crystals.

This is the case for scattering experiments. X-ray provides, after Fourier transform, only an isotropic radial distribution function. This smooth, structureless curve beyond medium-range order, can be reproduced numerically with a wide range of mutually inconsistent models. Such measurement can at most provide a way of eliminating bad models, but is useless as a tool for the positive identification among the other ones: any model that fails to produce a realistic RDF is clearly incorrect, this leaves, as shown using reverse Monte-Carlo, a wide range of incompatible models.

The experimental evidence for an isocoordinate rule in chalcogenide glasses provides yet another example of the difficulty of extracting microscopic information from these disordered materials. This rule states that for a given average coordination, samples with varying compositions will display identical properties. The isocoordinate rule has already been noted for a wealth of mechanical and thermal properties such as ultrasonic elastic constants, hole relaxation, and glass transition temperatures and hardness, and was found to hold for the more complex vibrational density of states : systems as different as Se<sub>40</sub>As<sub>60</sub> and Se<sub>55</sub>As<sub>30</sub>Ge<sub>15</sub>, with an average coordination of $`r=2.6`$, show a similar VDOS in the transverse accoustic (TA) region.

The vibrational isocoordinate rule (VIR) has, until now, only been checked experimentally, with the inherent limitations due to atomic species available and glass phase diagrams. This leaves a few questions open regarding the range of validity of this rule as well as its accuracy. In this paper, we present some results on a set of idealized models that provide a bound on these two questions.

Analytical study of this type of problem is difficult. Due to the vectorial nature of the problem, even simplified topologies such as the Bethe lattice are difficult to treat meaningfully. With the additional topological disorder, analytical solutions are beyond reach. We report here on the results of direct numerical simulations on a model system with simplified dynamics.

## II Details of the simulation

The simulations proceeded as follows. We start with a 4096-atom cell of Sillium – a perfectly tetravalent continuous-random network – constructed by Djordjevic et al. following the prescription of Wooten, Winer and Weaire; this network provides an idealized model with the appropriate initial topology. We then remove bonds at random in the network until we reach the desired concentration of 2-, 3- and 4-fold atoms. In the first stage of the simulation, we do not enforce any extra correlation and the final network corresponds to a perfectly random amorphous alloy. We then relax the network using a Kirkwood potential with interactions based on the table of neighbours, not on distance.

$$E=\frac{\alpha }{2}\underset{ij}{}(L_{ij}L_0)^2+\frac{\beta }{8}L_0^2\underset{ijk}{}\left(\mathrm{cos}\theta _{jik}+\frac{1}{3}\right)^2$$
(1)   
where $`\alpha `$ and $`\beta `$ are taken to be the same for all bonds and $`L_0`$ is the ideal bond length. We take a ratio of three-body to two-body force, $`\beta /\alpha =0.2`$, typical of tetrahedral semiconductors .

The resulting network is one of identical atoms except for the coordination. This is not too far from SeAsGe chalcogenides; because they sit side by side in the same row, these elements share very similar masses, elastic properties and Pauling electronegativities. As an additional simplification, we take the same tetrahedral angle for all triplets in the network. Real Se and As, in the respective 2- and 3-fold configuration, have angles that deviate from this value and tend towards 120 degrees. This simplification is less drastic than it appears because of the relatively low coordination, allowing a significant degree of flexibility in the network: angles can then be accomodated at very little elastic cost. A more serious concern is that although the 3 elements have very similar elastic constants in 4-fold environment, then bonding will get stronger as the coordination decreases. Comparison with experimental data shows that this effect shows up mostly in the high frequency TO peak. Moreover, because of the square root scaling, the deviation becomes apparent only between samples at the extreme of the composition scale.

To verify the isocoordinate rule, we prepare 3 different compositions at each average coordination from $`r=2.0`$ to $`3.0`$ (except at $`r=2.0`$, where only two different cells are created). We then proceed to distribute at random a desired proportion of 2-, 3- and 4–fold atoms. The three configurations typically correspond to (1) a configuration with a maximum of 3-fold atoms for the given average coordination, (2) one with a maximum of 4–fold, and (3) a composition between the two. For example, at $`r=3.0`$, we create a configuration with 50 percent of 2–old and 50 percent of 4–fold atoms, one with 25, 50 and 25 percent of 2-, 3-, and 4–fold atoms, respectively, and one with 100 percent of 3-fold atoms. This gives us the widest spectrum possible to study the VIR. Because we are not constrained by the glass forming diagram, this is also wider than what can be achieved experimentally.

After the topology has been determined, each sample is relaxed with the Kirkwood potential, using periodic boundary conditions. The dynamical matrix is then computed numerically on the fully relaxed configuration. This 12288 $`\times `$ 12288 matrix is then diagonalized exactly in order to obtain the full vibrational properties. The eigenvalues are binned and smoothed with a Gaussian of experimental width to provide the vibrational density of states presented in this paper.

We also introduce some chemical correlations to see how sensitive the VIR is to local fluctuations. We study here two types of correlations: phase separation – intoducing some king of homopolar preference – and mixing, with heteropolar bonds. A cost function is introduced in the bond-distributing sub-routine and all other phases of simulation remain the same.

## III Results and discussion

### A The vibrational isocoordinate rule

Figure 1 shows the vibrational density of state as a function of average coordination from $`r=2.0`$ to $`3.0`$. This distribution goes through the topological rigidity transition at $`r=2.4`$. First, we note that the VIR is approximately valid for two frequency bands: the transverse accoustic band – below $`f=0.7`$ and transverse optic band – above $`f=1.5`$. This holds for configurations with significant difference of composition, even configurations as different as the 100 percent 3-fold vs. 50-50 of 2- and 4–fold, show fairly similar VDOS in these regions. This is a wider application range than what was measured experimentally; the data reported by Effey and Cappelletti shows good overlap for the TA band but no consistent overlap in the higher frequency region of the VDOS. This is especially true of samples with widely different composition. The experimental shift in the TO peak seems to follow the concentration of Se. This is consistent with the expected increase in stiffness of the low coordinated atoms discussed above.

Taking this into account, a second look at the figures indicates clearly that the VIR is not an exact law. The structure of the TA peak in the configurations with $`r=3.0`$ shows significant variations following the concentration of 3-fold coordinated atoms. This shoulder, slightly above $`f=0.5`$, decreases in importance with the average coordination. This effect is not seen experimentally; the range of compositions for the real samples, however, is much narrower than that studied here.

Figure 1 also provides some indication about the relation between specific structures in the VDOS and the local environment. Because the VIR holds well, these are features that depend mostly weakly on the details of the composition and cannot be of much help in experimental situations. We have already mentioned the presence of additional modes related to 3-fold coordinated atoms on the high-frequency side of the TA band – a feature that is also present at high coordination in experimental measurement. Although this shoulder is significant, it represents the maximum impact it can have, with a direct comparison between a fully three-fold coordinated sample and one with zero such atoms. Given that the two network have a totally different topology, it is the similarity between the two curves rather than their differences that has to be emphasized.

The structure between the TA and the TO bands is more directly sensitive to the details of local structure, especially at low average coordination where more modes become localized. The structure around $`f=1`$ consistently represents the four-fold coordinated atoms. We can compare these structures to a fully four-fold structure (Fig. 2).

As we decrease the average coordination of the networks, we go through the topological rigidity threshold, at $`r=2.4`$. Below this value, the network becomes floppy and its macroscopic elastic constants vanish; local rigidity remains, however, and the VDOS is mostly unaffected except for a shift in the position of the peaks and an accumulation of modes at low frequencies. The signature of these zero-frequency modes is reported here in the backward peak formed at low frequencies and the accumulation at the lower-end of the TO peak in networks with large fraction of 2-fold coordinated atoms. The backward peak corresponds to spurious imaginary frequencies associated with floppy modes. Based on the theory of topological rigididity, these modes are localized above $`p_c`$ and span the whole network below this threshold.

The floppiness of the network is also reflected in the TO peak. Strikingly, the width of this peak is much more related to the overall coordination of the network than with local environment. From the work of Alben and Weaire, the TA peak has been associated with the overall coordination while the TO peak had been ascribed to the local tetrahedral symmetry. Vibrational density of states of fully four-fold cells generally gives a much wider if somewhat lower TO peak with, in the case of ill-coordinated networks, a very flat structure. Such a wide peak has generally been associated with non-tetrahedral environment but it is clear, based on the results obtained here, that the present of strain is also necessary. Even at $`r=3.0`$ the network contains enough floppy modes to relax a good part of the strain: the optical modes become then more localized and emerge as a relatively sharp feature at the edge of the vibrational spectrum.

As the averge coordination decreases the LA (around $`f=1.0`$) and LO ($`f=1.4`$) features also become more prominent. The first is particularly sensitive to the concentration of 4-fold atoms. This is especially clear at the lowest average coordination where this feature is totally absent in the Se<sub>80</sub>As<sub>20</sub> sample. At the same time, the LA peak is shifted upward to about $`f=1.15`$ and can therefore be associated with the presence of 3-fold atoms. This interpretation is in full agreement with the experimental results reported by Effey and Cappelletti.

### B Correlations

The above results are all for non-correlated samples. It is not impossible, however, that chemical ordering might take place in chalcogenide glasses. To address this question, we prepared, at $`r=2.6`$, two configurations of nominal Se<sub>40</sub>As<sub>60</sub> with full mixing -heteropolar bonds fully favored – and demixing – homopolar bonds preferred. In the first case, no 2-fold atom is bonded to another 2-fold atom. In the second case, clustering tends to take place. Figure 3 shows the VDOS for these two samples as compared with the non-correlated case already described in the previous section.

There is remarkably little impact on the spectrum. Although we see some broadening of the TA peak and a sharp structure at the far left of the TA peak in the demixed case, due to the very floppy selenium chains, the rest of the spectrum is essentially unchanged. Except, that is, for some shifting in the two peaks associated with the LA and LO peaks. Mixed environment seem to contribute more to the peak at 1.15 while demixed environments shift the peak to higher frequencies. The average of these two effects is manifest in the non-correlated spectrum. These changes in the spectrum are minor, however, and too subtle to allow any quantitative extraction from experimental data.

The choice of $`r=2.6`$ was based on some peculiar spectra found experimentally for Se<sub>2</sub>As<sub>3</sub>. Although we have been unable to reproduce the experimental behavior, we can conclude from this section that simple two-body correlation is not sufficient to provide the type of structure in the VDOS seen experimentally. More striking local changes need to occur, such as pseudo-molecular constructions, which give rise to localized modes.

## IV Conclusions

Following some interesting experiments displaying an isocoordinate rule for chalcogenide glasses, we studied the case of an ideal ternary glass consisting of identical atoms save for their coordination: same mass, same elastic constants same angular forces. It is then possible to examine the nature of this rule without interference from any other contribution to the vibrational density of state.

We have examined the isocoordinate rule at average concentrations varying from 2.0 to 3.0. What we find is that the isoccordinate rule is not an exact one. However there is much less variation of the vibrational density of state for a given average concentration, even as the type of atom is varied completely, with, for example, from totally three-fold to a mixture containing only 2 and 4-fold atoms than changing the overall concentration of atoms by 0.1 or 0.2.

Moreover, it appears that the VDOS is not very sensitive either to the presence of correlations. Changing considerably the local correlations affects very little even the qualitative structure of the VDOS.

All these results, in parallel with the experimental results obtained recently point to the fact that it is difficult to obtain positive information simply from the VDOS: if two samples have a different VDOS, it is clear that they diverge; nothing can be said, however if they have the same VDOS.

## V Acknowledgements

We thank Drs. Ronald Cappelletti and Birgit Effey for many stimulating discussions. NM thanks the NSF for support under Grant DMR 9805848, DAD thanks NSF for support under grants DMR 9618789 and DMR 9604921.

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