Theoretical study on molecules of interstellar interest. I. Radical cation of noncompact polycyclic aromatic hydrocarbons

Abstract

Polycyclic aromatic hydrocarbons (PAHs), in particular, their radical cation (PAH⁺), have long been postulated to be the important molecular species in connection with the spectroscopic observations in the interstellar medium. Motivated by numerous important observations by stellar as well as laboratory spectroscopists, we undertook detailed quantum mechanical studies of the structure and dynamics of electronically excited PAH+ in an attempt to establish possible synergism with the recorded data. In this paper, we focus on the quantum chemistry and dynamics of the doublet ground (X̃) and low-lying excited (Ã, B̃, and C̃) electronic states of the radical cation of tetracene, pentacene, and hexacene molecule. This study is aimed to unravel photostability, spectroscopy, and time-dependent dynamics of their excited electronic states. In order to proceed with the theoretical investigations, we construct suitable multistate and multimode Hamiltonians for these systems with the aid of extensive ab initio calculations of their electronic energy surfaces. The diabatic coupling surfaces are derived from the calculated adiabatic electronic energies. First principles nuclear dynamics calculations are then carried out employing the constructed Hamiltonians and with the aid of time-independent and time-dependent quantum mechanical methods. The theoretical results obtained in this study are found to be in good accord with those recorded in experiments. The lifetime of excited electronic states is estimated from their time-dependent dynamics and compared with the available data.