Open AccessLinkage Photoisomerization Mechanism in a Photochromic Ruthenium Nitrosyl Complex: New Insights from an MS-CASPT2 Study
Author(s) -
Francesco Talotta,
JeanLouis Heully,
Fabienne Alary,
Isabelle M. Dixon,
Leticia González,
Martial BoggioPasqua
Publication year - 2017
Publication title -
journal of chemical theory and computation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.001
H-Index - 185
eISSN - 1549-9626
pISSN - 1549-9618
DOI - 10.1021/acs.jctc.7b00982
Subject(s) - photoisomerization , intersystem crossing , ruthenium , photochromism , excited state , photochemistry , chemistry , isomerization , singlet state , linkage isomerism , metastability , density functional theory , chemical physics , computational chemistry , atomic physics , metal , physics , biochemistry , organic chemistry , catalysis
The N → O linkage photoisomerization mechanism in a ruthenium nitrosyl complex, [RuCl(NO)(py) 4 ] 2+ , for which a quasicomplete photoconversion between the stable nitrosyl (N-bonded) and metastable isonitrosyl (O-bonded) isomers has been observed under continuous irradiation of the crystal at 473 nm ( Cormary et al. Acta Cryst. B 2009 , 65 , 612 - 623 ), is investigated using multiconfigurational second-order perturbation theory (CASPT2). The results support efficient intersystem crossing pathways from the initially excited singlet states to the lowest triplet excited state of metal-to-ligand charge transfer character ( 3 MLCT). The topology of the involved potential energy surfaces corroborates a complex sequential two-photon photoisomerization mechanism involving nonadiabatic processes in agreement with experimental observations and previous density functional theory calculations.
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