Vibronic dephasing of anharmonic molecules. II. Impurity molecules isolated in lowhyphen;temperature matrices

摘要

The quantumhyphen;mechanical theory of vibronic dephasing presented in the first paper of this series is applied to the case of a diatomic impurity dissolved in a solid rarehyphen;gas host. An explicit expression for the pure dephasing rateT2prime;minus;1is derived in terms of microscopic properties of the impurity and host, and the effects of variations in the parameters characterizing these properties are investigated. The expression forT2prime;minus;1is applied specifically to the system Cl2/Ar in order to relate the results to those of previous classicalhyphen;trajectory calculations and of experimental measurements. The significance of anharmonicity in the intramolecular potential curve (of the impurity) is demonstrated.