Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

LA Rivera-Rivera and AF Wagner, INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 52, 979-989 (2020).

DOI: 10.1002/kin.21415

The vibrational and rotational mode-specific relaxations of CH(3)NO(2)with 50 kcal/mol of initial internal energy in an argon bath is computed at 300 K at pressures of 10-400 atm. This work uses archived information from our previously published J. Chem. Phys. 142, 014303 (2015) molecular dynamics simulations and employs our previous published J. Chem. Phys. 151, 034303 (2019) method for projecting time-dependent Cartesian velocities onto normal mode eigenvectors. The computed relaxations cover three types of energies: vibrational, rotational, and Coriolis. In general, rotational and Coriolis relaxations in all modes are initially fast followed by an orders of magnitude slower relaxation. For all modes, that slower relaxation rate is approximately comparable to the vibrational relaxation rate. For all three types of energies, there are small-scale mode-to-mode variations. Of particular prominence is the exceptionally fast relaxation shared in common by the external rotation about the C-N axis, the internal hindered rotation of the CH(3)group relative to the NO(2)group, and the symmetric stretch of the CH(3)group.

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