Anharmonic quantum contribution to vibrational dephasing

Physics – Chemical Physics

Scientific paper

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21 pages, 1 figure and 1 table

Scientific paper

10.1063/1.1766007

Based on a quantum Langevin equation and its corresponding Hamiltonian within a c-number formalism we calculate the vibrational dephasing rate of a cubic oscillator. It is shown that leading order quantum correction due to anharmonicity of the potential makes a significant contribution to the rate and the frequency shift. We compare our theoretical estimates with those obtained from experiments for small diatomics $N_2$, $O_2$ and $CO$.

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