Intramolecular Charge Transfer in 4-Aminobenzonitrile Does Not Need the Twist and May Not Need the Bend.
A study combining accurate quantum chemistry and full-dimensional quantum dynamics is presented to confirm the existence of an ultrafast radiationless decay channel from the charge-transfer state to the locally excited state in 4-aminobenzonitrile. This intramolecular charge-transfer pathway proceeds through a newly found planar conical intersection, and it is shown to be more efficient in the presence of acetonitrile than in the gas phase. Our results are consistent with recent experimental observations.
†Laboratoire de Chimie Physique (UMR 8000), CNRS, Université Paris-Sud, 91405 Orsay, France.|‡Institut Charles Gerhardt (UMR 5253), CNRS, Université de Montpellier, 34095 Montpellier, France.
Aurelie
A
Perveaux
§Departament de Quı́mica Fı́sica i Inorgànica, Universitat Rovira i Virgili, 43007 Tarragona, Spain.
Pedro J
PJ
Castro
†Laboratoire de Chimie Physique (UMR 8000), CNRS, Université Paris-Sud, 91405 Orsay, France.
David
D
Lauvergnat
§Departament de Quı́mica Fı́sica i Inorgànica, Universitat Rovira i Virgili, 43007 Tarragona, Spain.
Mar
M
Reguero
‡Institut Charles Gerhardt (UMR 5253), CNRS, Université de Montpellier, 34095 Montpellier, France.
Benjamin
B
Lasorne
aminobenzonitrile; conical intersection; internal conversion; intramolecular charge transfer; quantum chemistry; quantum dynamics; ultrafast radiationless decay