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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 7995-7999 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The inelastic neutron scattering spectrum of a sample of 1% CH4 in Ar was recorded in the energy range below 3 meV. Two strong quantum transitions at 0.90 and 0.59 meV and a broad distribution in the energy range up to 1.2 meV are found in the unannealed sample. Weaker transitions appear at 1.3, 1.7, and 2.2 meV, the latter with a shoulder at 2.3 meV. In the annealed sample (annealing temperature Ta=80 K, annealing time 1 h) the broad distribution and the line at 0.59 meV have disappeared. A new line at 0.45 meV and a shoulder at 0.77 meV merge from the broad distribution. The sharp transitions originate from CH4 molecules in well defined neighborhoods. They are attributed to molecules in an undisturbed fcc site (0.90, 1.3, and 2.2 meV), a fcc site neighboring a stacking fault (0.77 meV), an hcp site in hcp crystallites (0.59 meV), and hcp site within a single stacking fault (0.45 meV). Sites at grain boundaries, lattice distortions, etc., cause the broad background. The annealed sample still contains one stacking fault every 20 lattice planes.
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 2563-2575 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The inelastic incoherent neutron scattering technique has been applied in an energy range from 0.4 μeV to 60 meV to measure the rotational excitations of the methyl groups in polycrystals of CH3I, CH2DI, CD3I, CH3Br, CD3Br, and CH3Cl in a temperature range 5〈T[K]〈190. Tunnel splittings of the librational groundstate of 2.44 and 0.9 μeV were found for CH3I and CH3Br, respectively. Excitations to the higher excited librational states are identified via the temperature dependence and the isotope effects of the modes in the meV regime. The rotor–rotor coupling between neighboring methyl groups is found to be small. Thus single particle rotational potentials were derived from the observed eigenenergies. The potential strength increases going from the iodide via the bromide to the chloride. In CH3Br the rotational potential does not change on deuteration. In CH3I a very unusual increase in the rotational potential with deuteration is found. Besides the methyl librations, large amplitude motions around axes perpendicular to the molecular symmetry axis are observed at energies comparable to the methyl libration. The coupling of the methyl rotor to lattice modes modulating the strength of the orientational potential in CH3I gives rise to a peculiar temperature dependence of the tunnel splitting.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 5279-5285 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotational tunneling of methyl groups in Sn(CH3)4 molecules isolated in solid argon has been observed by inelastic neutron scattering at (h-dash-bar)ωt =72 μeV. In contrast to the bulk material all CH3 groups are equivalent, and the hindrance potentials is strongly reduced. The tunneling lines show an inhomogeneous broadening which decreases with decreasing concentration of the guest molecules. A discontinuity in the temperature dependence of the tunnel splitting could only be interpreted as due to a spontaneous rearrangement of the guest molecules in the argon lattice. Transitions at 2.1 and 20.7 meV are assigned to a methyl torsion on the basis of the temperature dependence of the tunneling lines and to a scelettal bending mode, respectively. A mode at 11.0 meV (88 cm−1) had not been found by other techniques. It is tentatively assigned to a libration of the Sn(CH3)4 against it cage. An alternative interpretation in a model of coupled methyl groups is also possible. The spectra become similar to the bulk material if the sample is annealed at T∼45 K indicating a clustering of the Sn(CH3)4 molecules to a not completely ordered phase.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 2204-2210 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The orientational disorder in a solid solution of methane and krypton (27% Kr) has been studied with inelastic neutron scattering. The spectra display a transition from diffusive high temperature rotations to rotational excitations of molecules with frozen-in orientational disorder at low temperatures. Of particular interest is a relatively sharp feature at an energy transfer of 0.78 meV which both broadens and shifts with increasing temperature. A simple model is based on a statistical distribution of local potentials due to the presence of Kr atoms and the state of excitation of the molecules. Finally, the isotope effect of the rotational excitations has been investigated.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 1313-1319 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: On the basis of the recently determined low temperature crystal structure the lattice dynamics of 2-butyne and a single particle methyl rotational potential are calculated using pair potential parameters given by Williams in 1974 within the model of semirigid molecules. In the regime of lattice modes the existence of four methyl librational bands with significant dispersion can explain the measured density of states. The single particle librational energy obtained for the rotational potential from the Schrödinger equation of the methyl rotor coincides well with the mean librational band energy. The calculated single particle tunneling frequency is only 17% lower than observed in experiment. Similarly well the activation energy is reproduced. Although the pair potential parameters developed for aromatic compounds need some scaling they are useful for materials with triple bond carbons. © 2002 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 6465-6473 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The perturbation of the partial orientational order in CH4II caused by dilution with Kr(xKr≤0.20) has been studied with inelastic incoherent neutron scattering. Both, the lines assigned as rotational tunneling and almost free molecular rotation, display a characteristic asymmetric broadening which gets more pronounced with increasing Kr concentration. At low Kr concentrations (xKr≤0.05) the tunneling spectra are well explained by a model which is based on a statistical distribution of local rotational potentials. In this model only the number of Kr atoms replacing orientationally ordered CH4 nearest neighbors is relevant for the local potential at the sites of tunneling molecules. The different local symmetries are not considered in the model. It was not possible to formulate a quantitative model for the scattering from molecules at nearly free rotor sites.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 5653-5661 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The crystal structure of α-phase toluene at 5 K has been refined from high resolution neutron powder diffraction data and the charge distribution in the molecule calculated ab initio. From these data, methyl rotational potentials of the two inequivalent methyl groups have been calculated for various parametrizations of transferable pair potentials and compared with potentials derived from tunneling and librational transitions. The results demonstrate that the inclusion of Coulomb interactions is necessary to reproduce the equilibrium orientations of the methyl groups. However, none of the model pair potentials yield the very strong sixfold contribution of the rotational potential of methyl group 1. The best approximation to the experimentally determined values is obtained with the pair potential parameters of Kitaigorodskii [Acta Crystallogr. 18, 585 (1965)]. However, by the inclusion of existing results on p-xylene, the average agreement obtained with the parametrization of Claverie [Acta Crystallogr. Part A 31, 448 (1975)] is equally good. Overall, it was found that general improvements can be made if the repulsive parts of the model pair potentials are softened. The presence of two inequivalent methyl groups in toluene which are influenced in different ways by the various contributions to the interaction provides a rigorous test of the modeling techniques.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 2052-2058 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: (CH4)cXe1−c systems with c=0.008, 0.015, 0.025, 0.1, and 0.9 have been investigated with inelastic neutron scattering. Tunnel transitions show almost free rotation of isolated CH4 quantum rotors at low methane concentrations and the appearance of dimers and trimers with increasing concentration. The rotational potential seen by a CH4 defect is explained by a model on the basis of statistical distributions of local orientational potentials. Disorder in a nonequilibrium matrix leads to a broad distribution of rotational potentials. A perturbed partially ordered phase II at large concentrations extends to higher concentrations than in CH4/Ar. No miscibility gap similar to that in CH4/Ar is found within the accessible concentration range c≤0.1 and c≥0.9.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 4838-4849 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Methane has been matrix isolated in solid Arc(N2)1−c, 0≤c≤1. Neutron spectra and diffractograms from identical samples are reported. In addition vapor-deposited argon and its mixtures with methane and nitrogen were studied by low temperature x-ray powder diffraction. The diffractograms and spectra were interpreted in terms of five different types of sites (I–V) in the vapor-deposited matrix after deposition at temperatures of 7–25 K. Shifts and broadenings of the methane tunneling spectra are caused by these sites: (I) Methane in regular fcc substitutional sites of solid pure argon or pure nitrogen in thermodynamic equilibrium shows nearly free rotation. The effective hindrance potential in nitrogen is lower than that in argon. In earlier IR-absorption work a site splitting of the vibrations was assigned as a splitting of the J=1 level of methane. INS shows that the latter is smaller than 0.030 meV. (II) Due to the nonequilibrium conditions during vapor-deposition, stacking faults and grains with hcp symmetry are formed both in pure argon and krypton, but not in pure nitrogen. Rather sharp lines in the methane spectra at 0.6 meV neutron energy transfer are assigned to such sites. (III) Argon and nitrogen form solid mixtures with an fcc structure in the argon rich phase (c≥0.45). By the addition of nitrogen the concentration of stacking faults and grains with hcp structure is enhanced. Both the peaks at 0.9 and at 0.6 meV are seen without major shift or broadening compared to the spectra of methane in pure argon. (IV) In nitrogen rich mixtures (c≤0.45) broad features in the energy range below 1 meV are observed. They are fitted by a simple mean field model.The fit shows that replacing of nitrogen next neighbors of a methane molecule by argon atoms strongly enhances the hindrance potential in this concentration range. (V) A major amount of the argon and krypton matrices is strongly distorted and has a very small coherence length. It is speculated that distorted zones are present as small clusters or on surfaces and small angle grain boundaries. The corresponding trapping sites for methane have a very low symmetry. A broad distribution of tunnel transitions around the elastic line occurs in samples which are, to a significant amount, composed of distorted lattices.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 5889-5890 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotational transitions of 1.5% CH4 isolated in a Kr matrix by condensing the mixed gas onto a cold (T=7 K) surface have been measured in the energy range 〈1.2 meV using a high resolution neutron scattering technique. The spectra are similar to those observed with CH4/ Ar. Most methane molecules are found at weakly disturbed substitutional fcc and hcp sites with weak rotational potentials. About 30% of the molecules are on disordered sites and display a broad distribution of stronger potentials.
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