Effective temperature representation of quantum delocalization effects on the dynamics of NO(A2Σ+←X2Π+) photoexcitation in Ne matrices
Abstract
The energetics of the optical excitation of the lowest Rydberg state of a nitric oxide molecule embedded in a neon matrix and the subsequent rearrangement of the solid host are investigated by classical molecular dynamics simulations. Quantum delocalization effects are incorporated through an effective temperature. The relevance of the inclusion of the anharmonicity of crystal site oscillations in the calculation of the effective temperature is evaluated. We show that representing zero point vibrations beyond the harmonic approximation improves the correspondence between the results of molecular dynamics simulations and pump–probe experiments performed on this system. We explored both the steady state