title: Time-dependent density functional theory study on direction-dependent electron and hole transfer processes in molecular systems.
abstract: We report on real-time time-dependent density functional theory calculations on direction-dependent electron and hole transfer processes in molecular systems. As a model system, we focus on α-sulfur. It is shown that time scale of the electron transfer process from a negatively charged S8molecule to a neighboring neutral monomer is comparable to that of a strong infrared-active molecular vibrations of the dimer with one negatively charged monomer. This results in a strong coupling between the electrons and the nuclei motion which eventually leads to S8ring opening before the electron transfer process is completed. The open-ring structure is found to be stable. The similar infrared-active peak in the case of hole transfer, however, is shown to be very weak and hence no significant scattering by the nuclei is possible. The presented approach to study the charge transfer processes in sulfur has direct applications in the increasingly growing research field of charge transport in molecular systems. © 2017 Wiley Periodicals, Inc.
authors.affiliation: Institute of Chemistry and Biochemistry, Physical and Theoretical Chemistry, Freie Universität Berlin, Takustr. 3, Berlin, 14195, Germany.
authors.forename: Pouya
authors.initials: P
authors.lastname: Partovi-Azar
authors.affiliation: Institute of Chemistry and Biochemistry, Physical and Theoretical Chemistry, Freie Universität Berlin, Takustr. 3, Berlin, 14195, Germany.
authors.forename: Payam
authors.identifier: 0000-0002-1541-7760
authors.initials: P
authors.lastname: Kaghazchi
keywords: ab initio molecular dynamics; charge transfer processes; maximally localized Wannier functions; molecular systems; time-dependent density functional theory; vibrational analysis