Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath

In our previous work [Rivera-Rivera et al., J. Chem. Phys. 142, 014303 (2015)], classical molecular dynamics simulations followed the relaxation, in a 300 K Ar bath at a pressure of 10-400 atm, of nitromethane (CH₃NO₂) instantaneously excited by statistically distributing 50 kcal/mol among all its internal degrees of freedom. Both rotational and vibrational energies decayed with nonexponential curves. The present work explores mode-specific mechanisms at work in the decay process. With the separation of rotation and vibration developed by Rhee and Kim [J. Chem. Phys. 107, 1394 (1997)], one can show that the vibrational kinetic energy decomposes only into vibrational normal modes, while the rotational and Coriolis energies decompose into both vibrational and rotational normal modes. The saved CH₃NO₂ positions and momenta were converted into mode-specific energies whose decay was monitored over 1000 ps. The results identify vibrational and rotational modes that promote/resist energy lost and drive nonexponential behavior.