Effect of nuclear motion on the absorption spectrum of dipicolinic acid

Abstract

Using semiclassical electron-radiation-ion dynamics, the authors have examined the effect of nuclear motion, resulting from both finite temperature and the response to a radiation field, on the line broadening of the excitation profile of 2,6-pyridinedicarboxylic acid (dipicolinic acid). With nuclei fixed, there is a relatively small broadening associated with the finite time duration of an applied laser pulse. When the nuclei are allowed to move, the excitation spectrum exhibits a much larger broadening, and is also reduced in height and shifted toward lower frequencies. In both cases, the excitation is due to well-defined pi to pi* transitions. The further inclusion of thermal motion at room temperature broadens the linewidth considerably because of variations in the molecular geometry: Transitions that had zero or negligible transition probabilities in the ground state geometry are weakly excited at room temperature.