Titel
Mechanism of Ultrafast Intersystem Crossing in 2-Nitronaphthalene
Abstract
Nitronaphthalene derivatives efficiently populate their electronically excited triplet states upon photoexcitation through ultrafast intersystem crossing (ISC). Despite having been studied extensively by time‐resolved spectroscopy, the reasons behind their ultrafast ISC remain unknown. Herein, we present the first ab initio nonadiabatic molecular dynamics study of a nitronaphthalene derivative, 2‐nitronaphthalene, including singlet and triplet states. We find that there are two distinct ISC reaction pathways involving different electronic states at distinct nuclear configurations. The high ISC efficiency is explained by the very small electronic and nuclear alterations that the chromophore needs to undergo during the singlet–triplet transition in the dominating ISC pathway after initial dynamics in the singlet manifold. The insights gained in this work are expected to shed new light on the photochemistry of other nitro polycyclic aromatic hydrocarbons that exhibit ultrafast intersystem crossing.
Stichwort
density functional calculationsintersystem crossing2-nitronaphthalenenon-adiabatic dynamicsphotophysics
Objekt-Typ
Sprache
Englisch [eng]
Persistent identifier
https://phaidra.univie.ac.at/o:1005818
Erschienen in
Titel
Chemistry - A European Journal
Band
24
Ausgabe
20
Seitenanfang
5379
Seitenende
5387
Verlag
Wiley
Erscheinungsdatum
2018
Zugänglichkeit
Rechteangabe
© 2018 The Authors

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