Test of the linear sum rule for vibrational energy transfer by trajectory calculations

Abstract

Vibrational relaxation rate constants for H2 in a bath of Ar are computed for v = 0, 4, 6, 10, and 13 and a rotational-translational temperature of 4500 K. The relaxation rate increases by a factor of 5.5 as v is raised from 0 to 10, then decreases by 33% as v is raised to 13. The v dependence of the vibrational relaxation violates a linear sum rule that is required to hold for an information theoretic synthesis of state-specific rate constants from bulk relaxation data.