Fluorescence of the perylene radical cation and an inaccessible D(0)/D(1) conical intersection: An MMVB, RASSCF, and TD-DFT computational study

Andrei M Tokmachev; Martial Boggio-Pasqua; David Mendive-Tapia; Michael J Bearpark; Michael A Robb

doi:10.1063/1.3278545

Fluorescence of the perylene radical cation and an inaccessible D(0)/D(1) conical intersection: An MMVB, RASSCF, and TD-DFT computational study

J Chem Phys. 2010 Jan 28;132(4):044306. doi: 10.1063/1.3278545.

Authors

Andrei M Tokmachev¹, Martial Boggio-Pasqua, David Mendive-Tapia, Michael J Bearpark, Michael A Robb

Affiliation

¹ Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom.

PMID: 20113032
DOI: 10.1063/1.3278545

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.