title: Fluorescence of the perylene radical cation and an inaccessible D(0)/D(1) conical intersection: An MMVB, RASSCF, and TD-DFT computational study.
abstract: The photophysics of the perylene radical cation (Pe(+)) was studied using the molecular mechanics-valence bond (MMVB) hybrid force field. Potential energy surfaces of the first three electronic states were investigated. Geometry optimizations of critical points-including conical intersections between the relevant electronic states-were performed using the MMVB analytical energy gradient for cations. No accessible planar conical intersection between the D(0) and D(1) states of Pe(+) was found; this is consistent with the experimentally observed D(1) lifetimes and the observation of D(1) emission from this cation in the condensed phase. Benchmark RASSCF and TD-DFT calculations support the reliability of the MMVB results.
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom.
authors.forename: Andrei M
authors.initials: AM
authors.lastname: Tokmachev
authors.forename: Martial
authors.initials: M
authors.lastname: Boggio-Pasqua
authors.forename: David
authors.initials: D
authors.lastname: Mendive-Tapia
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bearpark
authors.forename: Michael A
authors.initials: MA
authors.lastname: Robb