Cross-correlation trajectory study of vibrational relaxation of HF (v=1–7) by HF (v=0)

Results are presented for a three-dimensional quasiclassical trajectory study of the vibrational deactivation of vibrationally excited HF (v=1–7) by ground vibrational HF. A cross-correlation method of analysis is used to calculate probabilities and rate constants for V–V and V–RT transitions using trajectory results. Comparisons are made of calculated total deactivation rate constants (V–V plus V–RT) with experimental values. The V–RT dominates the relaxation for higher v states, and increases particularly rapidly with increasing v. Comparisons are made with recent classical-path calculations for this system, and in the use of Morse versus equivalent harmonic oscillator potentials.