Nonadiabatic photodynamics and UV absorption spectrum of all-trans-octatetraene

文献情報

出版日 2017-01-06

DOI 10.1039/C6CP07640H

インパクトファクター 3.676

著者

Igor Lyskov, Horst Köppel, Christel M. Marian

原文を見る

要旨

The short-time molecular quantum dynamics of all-trans-octatetraene after electronic excitation to the first bright valence state is theoretically investigated. A semiempirical approach of a multireference configuration interaction based on density functional theory, the so called hybrid DFT/MRCI, in both its original and redesigned formulations, is used for treating the electronic part of the problem. The nuclear kinetic part is defined with the help of symmetry-adapted internal coordinates also suitable for a large amplitude displacement. By incorporating ten in-plane and two out-of-plane nuclear degrees of freedom in the underlying Hamiltonian, the results of the time evolution of the excited wave packet are discussed. We show that the population transfer between the two coupled low-lying states in all-trans-octatetraene occurs in a 100–200 fs time regime. The calculated UV absorption spectra describe the main vibronic features correctly except for the band associated with the single-bond stretching motion which lacks intensity. The possible products of the photoisomerization in terms of symmetry-adapted coordinates are also discussed.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.