Rotational tunneling in a disordered system: nonequilibrium methane CN4 I1

M. PRAGER Institut fur Festkbrperjorschung der Kernforschutzgsanlage Julich, Posfach 1913, D-5170 Julich, West Germany Received July 2 1, 1987
This paper is dedicated to Professor J . A. Morrison

M. PRAGER. J. Chem. 66,570 (1988). Can. A pure methane sample was condensed onto a cold surface (T = 5 K) under conditions used in matrix-isolation spectroscopy. The sample shows a disturbed long range orientational order of CH4 11. The free rotor and tunneling transitions are considerably broadened. Stacking faults and defects are believed to cause the disorder. The disorder is largely reduced with increasing annealing temperatures Ta but, surprisingly, even at T, -- 0.7Tmthe long range order is not fully reestablished. M. PRAGER. J . Chem. 66,570 (1988). Can. On a condense un Cchantillon de mtthane pur sur une surface froide (T = 5 K), dans des conditions identiques i celles utilisees en spectroscopie par isolation en matrice. L'echantillon presente un ordre d'orientation i longue distance perturb6 de CH, 11. Les transitions dSes i la rotation libre et i l'effet tunnel sont trks Clargies. On considkre que des failles et des dCfauts dans l'empilement sont i l'origine du dCsordre. Le desordre est beaucoup moins important lorsqu'on augmente la temperature de recuisson, T,; toutefois, mkme lorsque Ta 0,7T,, on observe avec surprise que l'ordre i longue distance n'est pas complktement rCtabli. [Traduit par la revue]

I. Introduction Disorder is caused by the partial or complete loss of the three dimensional periodicity of a physical property. In classical glasses the relevant property is the center-of-mass position. In magnetic glassy systems the center of mass structure is still periodic but the magnetic periodicity is removed due to a statistical replacement of magnetic atoms by nonmagnetic ones. Glasses show universal low temperature properties, which are well described by the generally accepted "tunneling model". The physical structure of these tunneling states, however, is probably characteristic for every special system (1). In molecular solids orientational disorder can be produced if e.g. a part of the anisotropically interacting molecules is replaced by isotropic units (2-4). Usually for low concentrations of the isotropic species (4) and/or weak anisotropic coupling ( 9 , the effects of disorder can be considered as a perturbation of the ordered state. For highly diluted systems (6, 7), however, the long range orientational order can be completely removed, which in some cases is discussed under the aspect of an orientational glass (2) or "frozen-in" orientational disorder (3,4). There is the question whether pure molecular systems can be stabilized in an orientationally disordered state also. Long range orientational order can be disturbed if the solid is produced in a nonequilibrium procedure, e.g. by very fast cooling (analogous to glassy metals) or by condensing it from the gas phase onto a cold substrate directly in the solid phase. Such samples are used especially in the matrix-isolation spectroscopy technique to study individual molecules or molecular aggregates. They are known to be composed of small crystallites and to contain defects and stacking faults in rather large concentrations (8). Stacking faults lead to inequivalent molecular sites (fcc and hcp surrounding) and are often used to explain the spectroscopic observations (9). Defects interrupt the long range orientational interaction (as an isotropic impurity) and lead to a relaxed local orientational order. In the present work we tried to get an orientationally disordered sample using a matrix-isolation technique of preparation. In some materials the effect of disorder can be monitored via its influence on the quantum transitions of a weakly hindered rotor. Rotational tunneling, observable in various molecular

solids by incoherent neutron scattering, offers an extremely sensitive probe. Besides solid hydrogen (lo), methane is the most intensively studied quantum rotor system (1 1, 12). In thermal equilibrium methane first crystallizes in an fcc orientationally disordered phase, CH4 I. Below T, = 20.4 K the molecules partially order while the center of mass structure is unchanged. The ordering is caused by the octopole-octopole interaction (13). The topology is such that this interaction vanishes at 25% of the sites for symmetry reasons. These sites of 432 symmetry feel only a weak crystalline field and the methane molecules are almost free quantum rotors. The remaining 75% are orientationally ordered at sites of symmetry J2rn in a relatively strong rotational potential. Due to this potential one observes a tunnel splitting of the librational ground state with transitions at 75 and 140 p.eV. Both, free rotors (FR) and tunneling molecules (TM), will be affected by disorder but in different ways. The more sensitive probes certainly are the FR because the relaxation of orientations around a defect removes the compensation of the octopole-octopole interactions. The TM, on the other hand, will feel only a rather weak change of the basic potential.

11. Experiments and results Inelastic and elastic neutron scattering experiments were performed using light and heavy methane of 99.99% and 99% purity, respectively.
11.1. Sample preparation Both samples were prepared under similar conditions in the same special inlet system described elsewhere (14), which allows the condensation of large size matrix-isolation samples for neutron scattering experiments. A reference volume of 1 L was filled up to a pressure of 2 bar with CH4 or CD4. This volume is connected with the sample holder via a regulation valve. The inlet line is heated to T = 110 K up to the sample container consisting of A1 which was at T = 5 K. During condensation a very slow flux of 10 cm3/min was maintained. Thus the adsorbed methane had enough time to come close to thermal equilibrium with the cold surface despite the bad thermal conductivity of the matrix. The sample temperature during condensation was always below 15 K (see below).

11.2 Inelastic spectra The quantum rotor states of the methane molecules were measured using the high resolution neutron time-of-flight spectrometer IN5 of the Institut Laue-Langevin (ILL) in Grenoble. Two setups with energy resolutions of 34/59 peV FWHM at incident wavelengths of 8.516.0 A were used. Standard data corrections were performed and the measured spectra transformed into S(0,o) using the ILL-program package PRIME/CROSSX (15). Figure 1, bottom, shows the spectrum in the energy range up to 1.5 meV (Ai = 6 A) as taken immediately after condensation at a sample temperature T = 2 K. Various characteristic changes compared to equilibrium CH4 I1 are found: (i) The free rotor states at EFR = 1.09 meV are strongly suppressed and asymmetrically broadened to lower energy transfers. (ii) The tunneling transitions, sFown with better energy resolution in Fig. 2, bottom (Ai = 8.5 A), are also strongly asymmetric with the tail to higher energy transfer. (iii) The energy region between tunneling and free rotor lines contains a large number of new states. (iv) The energy levels are not in thermal equilibrium. A parametrization of the spectrum has been tried by using various lineshapes in potential space (Gaussian, Lorentzian, constant in a range, linear in a range, exponential, power-function, all may be asymmetric) to extract the intensities. The relation between rotational potentials V and quantum transition energy OTM,WFR was taken from Hiiller and Raich (16) for the TM [ l ] hwTM= 143 peV exp (0.0758(37 - V/B)) and was just extended phenomenologically to the FR-range as was done in ref. 6 [2] hwFR = 1.3 1 meV exp

CH411 matrix

energy t r a n s f e r (meV)
FIG.1. Inelastic neutron scattering spectra of condensed methane as measured with the high resolution time-of-flight spectrometer IN5 using a wavelength X i = 6 A (energy resolution 6E = 59 p,eV). Top: annealed at T , = 50 K for 30 min; bottom: not annealed. The nonzero background is an artefact due to an incomplete empty can subtraction.

-) : : : "(

where B is the rotational constant of a methane molecule. The solid lines in Figs. 1 and 2 are fits with asymmetric Lorentzians. The distributions of rotational potentials in the = = freshly prepared sample had widths of rFR 8 B and rTM6 B. Gaussians do not reproduce the large intensity between the tunneling and free rotor lines while constant lineshapes overemphasize it. Using the results from the fit with Lorentzians we see that the spin temperature T , describing the intensities of the FR lines is considerably higher (T, = (8 2 2) K) than the sample temperature T = 2 K . In the tunnel system the population of the E and T states relative to the A states corresponds to a spin temperature around T, -- 4 K. The spin temperature approaches somewhat the sample temperature with increasing annealing. However, all these numbers suffer from the problem that it is rather difficult to attribute the intensities of broad distributions unambiguously to FR and TM. At T = 10 K the described spectra have changed slightly, mainly by broadening. At T = 15 K we observe a broad quasielastic line beside the elastic line which is characteristic for rotational diffusion in CH4 I. Spectra taken during the condensation of the methane show an intermediate shape. No well-defined inelastic lines can be detected but the broad inelastic intensity is not yet quasi-elastic. The sample was annealed at temperatures Ta = 30, 50, 70 K for 30 min each. After each annealing, spectra were again measured at a sample temperature T = 2 K . Annealing at T = 30 K did not change the spectra. After heat treatment at T , = 50 K the tunneling lines are considerably sharpened and the free rotor lines get much more pronounced. The broad intensity between the free rotor and tunneling energies is reduced (Figs. 1 and 2,

top). The sharpening of the inelastic features in the spectrum further increases after annealing at Ta = 70 K. Although this temperature is only 22% below the melting point this annealing is not sufficient to produce an equilibrium CH4 I1 sample (17). 11.3Dirraction experiments To characterize the structure of our sample neutron powder ! diffraction patterns were measured using the diffractometer D 1 of the ILL, Grenoble, with an incoming wavtlength hi = 2.98 A in a range of momentum transfers 1.6 < Q (A-') < 3.3. Spectra were taken at three different temperatures T = 7, 15, 25 K from the unannealed sample and after annealing for 30 min at T , = 60 K . To get pronounced diffraction peaks, the coherent scatterer CD4 had to be used instead of CH4. Unfortunately, CD4 has a phase diagram somewhat different from that of CH, (for details see e.g. ref. 18). The pattern at T = 7 (15, 25) K are found, by comparison with earlier unpublished measurements, to be characteristic of phase I11 (11, I). We only show parts of the diffraction pattern taken at T = 7 K and 25 K before and after annealing (Fig. 3). The essential difference between the two spectra consists in a considerable sharpening of the lines originating from the methane sample. If one assumes that a finite crystal size causes the line broadening in the cold condensed sample on? estimates a characteristic diameter of the crystallites D = 400 A from the standard expression (19). [3] D

- "

112 COS

'PI

6 being the Bragg angle and p the vdW-radius of a methane molecule. Additional Bragg peaks are due to the A1 container and to N2

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probably condensed on the outer surface of our sample container.

111. Discussion The data we have presented on a one-component disordered quantum system would be difficult to obtain by methods other than INS. In particular, we have investigated: (i) Control of preparation conditions To prevent annealing of a matrix during condensation, very low condensation rates are usually used in the matrix production procedure. The temperature in the sample, however, cannot really be measured. In our system this is possible via an internal probe since the tunneling transitions of CH4 molecules show a characteristic temperature dependence in the range from He temperature to the phase transition temperature T, (1 1, 20) above which the molecule is orientationally disordered. Comparing the spectrum taken during condensation with those obtained later under conditions of thermal equilibrium we conclude that the sample temperature during preparation was T = (12 + 2) K, even for such large samples as necessary for neutron scattering experiments. Temperature gradients in the sample certainly affect somewhat the accuracy of this statement.
(ii) Perturbed long range orientational order and rotational potentials In spite of strong differences, the inelastic spectrum of the unannealed sample is qualitatively similar to spectra from CH4 I1 cooled down from the liquid. The crude diffraction patterns are also characteristic for long-range-ordered methane of the phases 111, 11, I. The finite linewidth of the Bragg peaks can be attributed to finite crystallite sizes. Thus it seems possible that surface effects are influencing the rotational potentials. If one assumes that they are significant in a depth of about 3 molecular diameters below the surface one expects, from the relative volumes, disorder for 5% of the molecules. This is much smaller than the observed value. We note that in particular the free rotor states which in an undisturbed lattice represent already 25% of the molecules are nearly completely suppressed. Thus, the disorder must be of different origin. The matrices used in matrix isolation spectroscopy are known to represent nonequilibrium states, containing stacking faults, dislocations, and so on (8, 9). In methane, rather low concentrations of such statistically distributed defects will remove the compensation of the octopoleoctopole interaction at the FR sites and modify the potential strengths at the tunneling sites. The general effects on the spectra thus should be similar to those found in the system CH4/Kr where the anisotropic octopole-octopole interaction between methane molecules is diluted by some percentages of isotropic Kr atoms (4). Indeed, the spectra resemble each other but there are also differences. In the mixed CH4/Kr sample the distinction between FR and tunneling states, both weighted according to the probabilities found in the undisturbed lattice, could be maintained up to rather large Kr concentrations (CK, = 0.1) while the disorder in the present cold condensed sample strongly suppresses the FR states ccmpared to the TM. The system thus seems to be closer to a fully disordered state. It is a question whether an orientational "glassy state" can be described by a general distribution function as in the tunneling standard model (STM) of normal glasses (21). There must be some fundamental differences, however. It is a symmetry property of rotational potentials that their minima are equivalent. This means an asymmetry parameter, called A is the STM, is always zero. On the other hand, the tunneling parameter A is

-400

0
energy transfer (peV)

400

FIG. 2. Inelastic neutron scattering spectra of condensed methane. Spectrometer: IN5. Xi = 8.5 A (6E = 34 keV). Top: annealed at T, = 50 K for 30 min; bottom: not annealed. The nonzero background is an artefact due to an incomplete empty can subtraction.

scattering angle 2 0

(O)

FIG.3. Neutron diffraction patterns of condensed methane CD4 in the range of the (111) and (200) reflections as measured with the powder diffractometer Dla of the ILL with a wavelength X i = 2.98 A. The shaded peaks are due to a N2 surface contamination. Left: T = 25 K, CD4I; right: T = 7 K , CD4 111. Top: Sample annealed at T, = 60 K for 30 rnin; bottom; Sample not annealed.

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related to the potential strength V since the tunneling frequency depends almost exponentially on V according to [ I ] . A possible function for molecular system analogous to the STM thus would read simply [4] p(V) dV = constant dV and yields a distribution of tunneling splittings [51 p(w,)a exp (- PV) In some matrix isolation systems we have indeed found a distribution compatible with [5]. The tunneling states are o b s e ~ e d as wings close to the elastic line. The shape of this spectrum remained unchanged if the instrumental resolution was improved (22). In the present case, however, such a distribution function is not able to describe the spectra. Instead rather broad Lorentzians in potential space with cutoffs at the free rotor energy on the one side and at the tunneling energy on the other yield the best fits. (iii) InJluence of disorder on the phase diagram Due to the presence of disorder the phase diagram of methane is somewhat changed. While the equilibrium sample shows the phase transition to orientationally disordered CH4 I at T, = 20.4 K, we o b s e ~ already the quasielastic spectra corresponding to e disordered methane at T = 15 K. Thus the phase transition temperature T, is lowered by more than 25% due to disorder, as in the CH4/Kr mixtures (4). The diffraction patterns reflect the same effect for CD4. We did not try, however, to get more accurate values of the transition temperatures. (iv) Effects of annealing With increasing annealing the inelastic intensity is more and more concentrated into the FR and tunneling lines, which have grown much sharper. But even after annealing at T, = 7 0 K the spectrum reflects disorder. The inelastic lines still have asymmetric tails and the intensity of the FR transitions is still considerably below the 25% of the inelastic scattering measured for an equilibrium structure of CH4 11. The remaining defects clearly have to overcome rather large activation barriers. This is in contrast to the assumption that the onset of diffusion fully reconstructs a matrix at annealing temperatures T, = 0.4T,,. With annealing, the size of the methane crystallites has considerably increased, yielding sharp Bragg peaks. All these effects prove that the disorder in our system is not due to surface effects. (v) Spin conversion In the unannealed and the annealed matrix the quantum rotor levels, especially the FR, are not in thermal equilibrium with the lattice. While in disordered CH4/Kr mixtures with rather large Kr concentrations spin conversion is accelerated (23), this seems to be not the case for the matrix system. Thus, it is not the disorder but the presence of Kr atoms that must be responsible for the effect in the CH4/Kr system. The deviation from the thermal equilibrium, however, is also different to that of quenched CH4 I1 (24). In the quenched material E-state molecules do not convert, while in our matrix an increased population of T-states is found. This o b s e ~ a t i o n however, needs a , more detailed study. The interpretation of the present spectra arising from a threedimensionally-coupled, disordered quantum rotor system must remain incomplete. Theoretical models usually use a molecular field theory to describe the system in a single-particle picture and hence cannot explain the present o b s e ~ a t i o n sHere compu.

ter simulation seems to be possible and helpful for a deeper understanding of our data. The single-particle picture is certainly more adapted to single molecular defects in an atomic matrix. Thus, complementary information can be obtained by investigating CH4 matrixisolated in rare gases. Such experiments were already performed with limited energy resolution and for equilibrium samples (5). In a cold condensed sample several transitions belonging to inequivalent sites (9,25) and an additional broad distribution of states is found (25). This is direct evidence for the existence of the defects used to explain the present results.

IV. Conclusions
Methane condensed slowly (10 cm3/min) onto a cold surface (T = 5 K) maintains a long range orientational structure as in CH4 I1 but displays orientational disorder, which manifests itself in a significant broadening and weakening of the quantum transitions compared to the undisturbed material. In the disturbed structure the transition temperature into the orientationally ordered phase I1 is reduced by more than 25%. The disorder shows remarkable differences to that produced by diluting the orientation-dependent interaction with small percentages of rare gases. 'The free rotor states are strongly suppressed and represent more a broad band of states at energies below that of the free rotor, but no system with random orientations is formed. The disorder, most probably, is caused by stacking faults and defects and is considerably reduced with increasing annealing. Surprisingly even at the highest annealing temperatures T,/T,, 0.7 it could not be completely removed.

Acknowledgements
W. Langel made available his matrix isolation setup. H. Blank and G. Kearly helped with the experiments on IN5. A. Hewat provided measuring time for a short run on D l a . H. Lauter supplied the CH4. I thank all these colleagues for their collaboration. 1. U. BUCHENAU, PRAGER, NUCKER, J. DIANOUX, M. N. A. N. AHMAD, W. A. PHILLIPS. and Phys Rev. B 34,5665 (1986). 2. A. B. HARRIS H. MEYER. J. Phys. 63, 3 (1985). and Can. 3. W. PRESS, JANIK, H. GRIMM. Phys. B 49,9 (1982). B. and Z. 4. S. GRONDEY, PRAGER, W. PRESS. Chem. Phys. 86, M. and J. 6465 (1987). W. and In 5. Y. KATAOKA, PRESS,U. BUCHENAU, H. SPITZER. Neutron inelastic scattering 1977. Vol. 1. IAEA, Vienna. 1978. p. 311. 6. S. GRONDEY, PRAGER, PRESS, A. HEIDEMANN. M. W. and J. Chem. Phys. 85,2204 (1986). 7. F. DE LUCA B. MARAVIGLIA. Lett. 101,300 (1983). and Phys 8. S. CRADOCK A. J. HINCHCLIFFE. isolation. Cambridge and Matrix University Press, Cambridge, London, New York, Melbourne. 1975. 9. L. H. JONES, A. EKBERG, B. I. SWANSON.Chem. Phys. S. and I. 85,3203 (1986). 10. I. F. SILVERA. Mod. Phys. 52,393 (1980). Rev. 11. W. PRESS. Single particle rotations in molecular crystals. Springer tracts in modem physics. Vol. 92. Springer, Berlin, Heidelberg, New York. 1981. 12. Y. OZAKI, KATAOKA, Y. andT. YAMAMOTO. J. Chem. Phys. 73, 3442 (1980). 13. H. M. JAMES T. A. KEENAN. Chem. Phys. 31,12 (1959). and J. H. and J. Phys. 14. W. LANGEL, KOLLHOFF, E. K N ~ ~ Z I N G E R . E 19, 86 (1986). 15. R. E. GOSH. Intemal Technical Report. 1975. ILL 16. A. HULLER J. RAICH. Chem. Phys. 71,3851 (1979). and J.

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17. A. HEIDEMANN, PRESS,K. J. LUSHINGTON, J. A. W. and MORRISON. Chem. Phys. 75,4003 (198 1). J. 18. M. PRAGER, PRESS,A. HEIDEMANN, C. VETTIER.J. W. and Chem. Phys. 77,2577 (1982). In 19. C. J. BROWN. X-Ray diffraction by polycrystalline materials. Edited b y H. S. Peiser, H. P. Rooksby, and A. J. C. Wilson. Chapman and Hall, London, New York. 1960. 20. W. PRESS and A. KOLLMAR. Solid State Commun. 17, 405 (1975).

In 21. W. HUNKLINGER M. V . SCHICKFUS. Amorphous solids. and Edited b y W. A. Phillips. Topics in Current Physics, Vol. 24. Springer, Berlin, Heidelberg, New York. 1981. Unpublished results. 22. W. LANGEL M. PRAGER. and J. 23. P. CALVANI H. GLATTLI. Chem. Phys. 83, 1822 (1985). and K. J. K. 24. A. HEIDEMANN, J. LUSHINGTON, A . MORRISON, J. NEUMAIER, W. PRESS. Chem. Phys. 81,5799 (1984). and and Unpublished results. 25. M. PRAGER W. LANGEL.