The threshold region of vibrational energy redistribution (IVR) presents a great experimental and computational challenge for organic molecules with more than 10 degrees of freedom. The density of states ρtot is high and requires high resolution measurements over a wide range to cover all relevant timescales experimentally. Yet ρtot is sufficiently low that IVR quantities like the initial relaxation time τIVR or the number of participating states Neff are very sensitive to the coupling structure. To highlight the competing effects of molecular symmetry and mode localization on the accessible density of states, this work complements a study of benzene (Callegari, A., Merker, U., Engels, P., Srivastava, H. K., Lehmann, K. K., and Scoles, G., 2000, J. chem. Phys., 113, 10583) by measuring the CH overtone spectra of pyrrole (C4H4NH) and 1,2,3-triazine (C3N3H3) using eigenstate-resolved double-resonance spectroscopy. Large scale computations of IVR dynamics were undertaken, applying filter diagonalization to analytically fitted fourth-order ab initio force fields. With an overall adjustment to the anharmonicity of the potential, the modelled Neff and τIVR agree with the experimental quantities within a factor of 2 to 3, which is reasonable for a rate theory in the threshold regime. The models also correctly predict the experimentally observed trends of τIVR and Neff for the two molecules, and provide insight into the highly off-resonant coupling mechanism, which yields very sharp linewidths.
ASJC Scopus subject areas
- Molecular Biology
- Condensed Matter Physics
- Physical and Theoretical Chemistry