Quantum dynamics studies of the photodissociation of molecular systems

[摘要] The focus of the work presented here is the theoretical description of the photodissociation of molecular systems possessing low-lying singlet 3s/\(\pi\)σ* states that are quasi-bound with respect to an N-H bond. Model Hamiltonians are developed for and subsequently used in quantum dynamics simulations of the photo-induced dynamics of the molecules ammonia, 3-pyrroline, pyrrole, and aniline. The origin to the barrier to dissociation in ammonia's first excited state is identified and the effect of vibronic coupling of this state to a number of higher-lying states on the dissociation dynamics of the molecule is assessed. A conformer-resolved study of the dynamics of 3-pyrroline following excitation into its first two excited states is performed, and the first two bands in its electronic spectrum are calculated and analysed. The first band in the electronic spectrum of pyrrole is calculated, its vibrational structure assigned and the role played by intensity borrowing in its formation analysed. The dynamics of aniline following excitation to its first to singlet \(\pi\)\(\pi\)* are studied. Two previously neglected 3p Rydberg states are found to play important roles in aniline's excited state dynamics. The first two bands in aniline's electronic absorption spectrum are calculated, and the role played by the Hertzberg-Teller effect in the first band is analysed

[发布机构] University:University of Birmingham;Department:School of Chemistry

[关键词] Q Science;QD Chemistry