Structure and dynamics of electronically excited molecular systems

Abstract

Structure and dynamics of electronic excited states of molecular systems is of contemporary interest to understand a rich variety of processes ranging from molecular spectroscopy to reaction dynamics. Developments over the past decades have established that coupling of electronic and nuclear motion is a generic feature in polyatomic molecular systems which causes a breakdown of the Born–Oppenheimer approximation. Such a coupling leads to conical intersections in non-linear and glancing degeneracy in linear polyatomic systems. While the former case is quite general and has wide variances depending on the nature of the coupling on the symmetry ground, the latter one is specific to the linear systems having axial symmetry. The Jahn–Teller (JT) systems form a subclass in the former category and the latter category constitutes the Renner–Teller (RT) systems. These systems are characterized by high point group symmetry and orbital degeneracy. The latter splits upon distortion along suitable symmetry reducing nuclear displacement. The JT or the RT split component states may undergo symmetry allowed coupling among another JT or RT split component states or with some non-degenerate states. These are termed as the pseudo-JT and pseudo-RT coupling, respectively. We have studied a variety of photo-induced molecular processes with the aid of ab initio quantum chemistry and first principles quantum dynamics methods. We will document here some of the important developments in the field focusing on the work done on the JT and RT systems primarily in our own laboratory. This article is categorized under: Theoretical and Physical Chemistry > Spectroscopy Software > Quantum Chemistry Structure and Mechanism > Molecular Structures.