A study of methyl reorientation in solid nitromethane by neutron scattering

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Abstract
The geometrical and dynamical properties of the reorientation of the methyl group of nitromethane in the solid state have been studied by inelastic neutron scattering. Quasielastic scattering spectra have been obtained for several values of momentum transfer at five temperatures between 50° and 150 °K. The spectra are shown to be consistent with jumps of 120 ° about an axis coincident with the C–N bond. The temperature dependence of the residence time yields a barrier of 234 cal/mole. An inelastic neutron spectrum obtained at 4.2 °K suggests a tunnel splitting of the torsional ground state of 0.045±0.005 meV, which is consistent with the derived activation energy. Inelastic neutron scattering has also been used to determine the energy of the tunnel split first excited state which in CH3NO2 has a mean energy of 7.4 meV above the ground state and is split by 1.8 meV. In the deuterated compound, the first excited stated is at 5.3 meV above the ground state and its splitting is less than the instrumental resolution.