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Excited state potential energy surfaces of bistridentate Ru-II complexes - A TD-DFT study

Österman, Tomas LU and Persson, Petter LU (2012) In Chemical Physics 407. p.76-82
Abstract
Time-dependent density functional theory (TD-DFT) calculations have been used to investigate low-energy singlet and triplet excited state potential energy surfaces (PES) of two prototype Ru-II-bistridentate complexes: [Ru-II(tpy)(2)](2+) (tpy is 2,2':6',2 ''-terpyridine) and [Ru-II(dqp)(2)](2+) (dqp is 2,6-di(quinolin-8-yl)pyridine). Solvent effects were considered using a self-consistent reaction field scheme. The calculations provide information about the excited state manifold along pathways for activated decay of metal-to-ligand charge-transfer (MLCT) excited states via metal-centered (MC) states for the two complexes. Significant differences in the energy profiles of the investigated PESs are explained through characterization of the... (More)
Time-dependent density functional theory (TD-DFT) calculations have been used to investigate low-energy singlet and triplet excited state potential energy surfaces (PES) of two prototype Ru-II-bistridentate complexes: [Ru-II(tpy)(2)](2+) (tpy is 2,2':6',2 ''-terpyridine) and [Ru-II(dqp)(2)](2+) (dqp is 2,6-di(quinolin-8-yl)pyridine). Solvent effects were considered using a self-consistent reaction field scheme. The calculations provide information about the excited state manifold along pathways for activated decay of metal-to-ligand charge-transfer (MLCT) excited states via metal-centered (MC) states for the two complexes. Significant differences in the energy profiles of the investigated PESs are explained through characterization of the electronic properties of the involved states calculated by the TD-DFT calculations. Finally, implications of the computational results for the design of octahedral metal complexes utilizing ligand field splitting (LFS) strategies for efficient light-harvesting in photochemical applications such as artificial photosynthesis are discussed. (C) 2012 Elsevier B. V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Ru-II complexes, Time-dependent density functional theory, Potential, energy surfaces, Excited state lifetimes
in
Chemical Physics
volume
407
pages
76 - 82
publisher
Elsevier
external identifiers
  • wos:000310570700010
  • scopus:84868203538
ISSN
0301-0104
DOI
10.1016/j.chemphys.2012.09.001
language
English
LU publication?
yes
id
8827e4a3-5e2a-4040-9795-08c61ca0ab5f (old id 3276230)
date added to LUP
2012-12-20 14:17:23
date last changed
2017-09-03 04:05:22
@article{8827e4a3-5e2a-4040-9795-08c61ca0ab5f,
  abstract     = {Time-dependent density functional theory (TD-DFT) calculations have been used to investigate low-energy singlet and triplet excited state potential energy surfaces (PES) of two prototype Ru-II-bistridentate complexes: [Ru-II(tpy)(2)](2+) (tpy is 2,2':6',2 ''-terpyridine) and [Ru-II(dqp)(2)](2+) (dqp is 2,6-di(quinolin-8-yl)pyridine). Solvent effects were considered using a self-consistent reaction field scheme. The calculations provide information about the excited state manifold along pathways for activated decay of metal-to-ligand charge-transfer (MLCT) excited states via metal-centered (MC) states for the two complexes. Significant differences in the energy profiles of the investigated PESs are explained through characterization of the electronic properties of the involved states calculated by the TD-DFT calculations. Finally, implications of the computational results for the design of octahedral metal complexes utilizing ligand field splitting (LFS) strategies for efficient light-harvesting in photochemical applications such as artificial photosynthesis are discussed. (C) 2012 Elsevier B. V. All rights reserved.},
  author       = {Österman, Tomas and Persson, Petter},
  issn         = {0301-0104},
  keyword      = {Ru-II complexes,Time-dependent density functional theory,Potential,energy surfaces,Excited state lifetimes},
  language     = {eng},
  pages        = {76--82},
  publisher    = {Elsevier},
  series       = {Chemical Physics},
  title        = {Excited state potential energy surfaces of bistridentate Ru-II complexes - A TD-DFT study},
  url          = {http://dx.doi.org/10.1016/j.chemphys.2012.09.001},
  volume       = {407},
  year         = {2012},
}