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Linkage Photoisomerization Mechanism in a Photochromic Ruthenium Nitrosyl Complex: New Insights from an MS-CASPT2 Study.
- Source :
-
Journal of chemical theory and computation [J Chem Theory Comput] 2017 Dec 12; Vol. 13 (12), pp. 6120-6130. Date of Electronic Publication: 2017 Nov 28. - Publication Year :
- 2017
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Abstract
- The N → O linkage photoisomerization mechanism in a ruthenium nitrosyl complex, [RuCl(NO)(py) <subscript>4</subscript> ] <superscript>2+</superscript> , 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 ( <superscript>3</superscript> 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.
Details
- Language :
- English
- ISSN :
- 1549-9626
- Volume :
- 13
- Issue :
- 12
- Database :
- MEDLINE
- Journal :
- Journal of chemical theory and computation
- Publication Type :
- Academic Journal
- Accession number :
- 29136470
- Full Text :
- https://doi.org/10.1021/acs.jctc.7b00982