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Nonadiabatic Dynamics Simulation Predict Intersystem Crossing in Nitroaromatic Molecules on a Picosecond Time Scale
Author(s) -
Zobel J. Patrick,
González Leticia
Publication year - 2019
Publication title -
chemphotochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.13
H-Index - 18
ISSN - 2367-0932
DOI - 10.1002/cptc.201900108
Subject(s) - intersystem crossing , picosecond , internal conversion , singlet state , chemical physics , molecule , photochemistry , chemistry , chemical dynamics , molecular physics , physics , computational chemistry , atomic physics , excited state , quantum mechanics , electron , laser
Previous time‐resolved spectroscopic experiments and static quantum‐chemical calculations attributed nitronaphthalene derivatives one of the fastest time scales for intersystem crossing within organic molecules, reaching the 100 fs mark. Nonadiabatic dynamics simulations on three nitronaphthalene derivatives challenge this view, showing that the experimentally observed ∼100 fs process corresponds to internal conversion in the singlet manifolds. Intersystem crossing, instead, takes place on a longer time scale of ∼1 ps. The dynamics simulations further reveal that the spin transitions occur via two distinct pathways with different contribution for the three systems, which are determined by electronic factors and the torsion of the nitro group. This study, therefore, indicates that the existence of sub‐picosecond intersystem crossing in other nitroaromatic molecules should be questioned.