Measurement and ab initio modeling of the inelastic neutron scattering of solid N-methylformamide

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Abstract
Vibrational motions of solid N-methylformamide (NMF) and its N-deuterated analogue are investigated using the inelastic neutron scattering (INS) technique at 15 K. The force field for obtaining the normal vibrational modes of the crystal is based on a quantum chemical calculation and a subsequent transfer of a harmonic force field of a smaller pentameric segment to a fragment of 11 NMF molecules. Two types of hydrogen bonds present in crystalline NMF are also modeled with dimers. The distinct bonding leads to a splitting of the N-hydrogen wagging mode in the spectrum. Although the hydrogen bonding has a profound effect on vibrational frequencies, the results indicate that an occurrence of a double-well potential for bonded hydrogen proposed previously is unlikely. Instead, a limited electronic conjugation along the hydrogen bonds in crystalline NMF is observed. Unlike in previous models, we simulate the relative INS intensity of each vibrational transition separately, which leads to a substantial improvement of the overall profile of the intensity pattern. The modeling allows one to assign most of observed INS bands to vibrational modes and the overall spectral profile that reproduced by the simulation compares well with the experiment.