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Exploring Photoinduced Excited State Evolution in Heterobimetallic Ru(II)-Co(III) Complexes

Kuhar, Korina; Fredin, Lisa LU and Persson, Petter LU (2015) In The Journal of Physical Chemistry Part B 119(24). p.7378-7392
Abstract
Quantum chemical calculations provide detailed theoretical information concerning key aspects of photoinduced electron and excitation transfer processes in supramolecular donor-acceptor systems, which are particularly relevant to fundamental charge separation in emerging molecular approaches for solar energy conversion. Here we use density functional theory (DFT) calculations to explore the excited state landscape of heterobimetallic Ru-Co systems with varying degrees of interaction between the two metal centers, unbound, weakly bound, and tightly bound systems. The interplay between structural and electronic factors involved in various excited state relaxation processes is examined through full optimizations of multiple charge/spin states... (More)
Quantum chemical calculations provide detailed theoretical information concerning key aspects of photoinduced electron and excitation transfer processes in supramolecular donor-acceptor systems, which are particularly relevant to fundamental charge separation in emerging molecular approaches for solar energy conversion. Here we use density functional theory (DFT) calculations to explore the excited state landscape of heterobimetallic Ru-Co systems with varying degrees of interaction between the two metal centers, unbound, weakly bound, and tightly bound systems. The interplay between structural and electronic factors involved in various excited state relaxation processes is examined through full optimizations of multiple charge/spin states of each of the investigated systems. Low-energy relaxed heterobimetallic states of energy transfer and excitation transfer character are characterized in terms of energy, structure, and electronic properties. These findings support the notion of efficient photoinduced charge separation from a Ru(II)-Co(III) ground state, via initial optical excitation of the Ru-center, to low-energy Ru(III)-Co(II) states. The strongly coupled system has significant involvement of the conjugated bridge, qualitatively distinguishing it from the other two weakly coupled systems. Finally, by constructing potential energy surfaces for the three systems where all charge/spin state combinations are. projected onto relevant reaction coordinates, excited state decay pathways are explored. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
119
issue
24
pages
7378 - 7392
publisher
The American Chemical Society
external identifiers
  • wos:000356754800027
  • scopus:84934992110
ISSN
1520-5207
DOI
10.1021/jp510950u
language
English
LU publication?
yes
id
e3e59790-1f43-43b3-bf62-ef4760459c00 (old id 7790889)
date added to LUP
2015-09-03 09:22:24
date last changed
2017-09-03 04:13:47
@article{e3e59790-1f43-43b3-bf62-ef4760459c00,
  abstract     = {Quantum chemical calculations provide detailed theoretical information concerning key aspects of photoinduced electron and excitation transfer processes in supramolecular donor-acceptor systems, which are particularly relevant to fundamental charge separation in emerging molecular approaches for solar energy conversion. Here we use density functional theory (DFT) calculations to explore the excited state landscape of heterobimetallic Ru-Co systems with varying degrees of interaction between the two metal centers, unbound, weakly bound, and tightly bound systems. The interplay between structural and electronic factors involved in various excited state relaxation processes is examined through full optimizations of multiple charge/spin states of each of the investigated systems. Low-energy relaxed heterobimetallic states of energy transfer and excitation transfer character are characterized in terms of energy, structure, and electronic properties. These findings support the notion of efficient photoinduced charge separation from a Ru(II)-Co(III) ground state, via initial optical excitation of the Ru-center, to low-energy Ru(III)-Co(II) states. The strongly coupled system has significant involvement of the conjugated bridge, qualitatively distinguishing it from the other two weakly coupled systems. Finally, by constructing potential energy surfaces for the three systems where all charge/spin state combinations are. projected onto relevant reaction coordinates, excited state decay pathways are explored.},
  author       = {Kuhar, Korina and Fredin, Lisa and Persson, Petter},
  issn         = {1520-5207},
  language     = {eng},
  number       = {24},
  pages        = {7378--7392},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Exploring Photoinduced Excited State Evolution in Heterobimetallic Ru(II)-Co(III) Complexes},
  url          = {http://dx.doi.org/10.1021/jp510950u},
  volume       = {119},
  year         = {2015},
}