Re and Br X-ray Absorption Near-Edge Structure Study of the Ground and Excited States of [ReBr(CO)3(bpy)] Interpreted by DFT and TDDFT Calculations
Result description
X-ray absorption spectra of fac-[ReBr(CO)3(bpy)] near the Re L3- and Br K-edges were measured in a steady-state mode as well as timeresolved at 630 ps after 355 nm laser pulse excitation. Relativistic spinorbit time-dependent density functional theory (TD-DFT) calculations account well for the shape of the near-edge absorption (the "white line") of the ground-state Re spectrum, assigning the lowest-lying transitions as core-toligand metal-to-ligand charge transfer from Re 2p3/2 into predominantly ?*(bpy) molecular orbitals (MOs) containing small 5d contributions, followed in energy by transitions into ?* Re(CO)3 and delocalized ?*/?* MOs. Transitions gain their intensities from Re 5d and 6s participation in the target orbitals. The 5d character is distributed over many unoccupied MOs; the 5d contribution to any single empty MO does not exceed 29%. The Br K-edge spectrum is dominated by the ionization edge and multiple scattering features, the pre-edge electronic transitions being very
Keywords
carbonyl-bipyridine complexesdensity functional theoryorder regular approximation
The result's identifiers
Result code in IS VaVaI
Result on the web
DOI - Digital Object Identifier
Alternative languages
Result language
angličtina
Original language name
Re and Br X-ray Absorption Near-Edge Structure Study of the Ground and Excited States of [ReBr(CO)3(bpy)] Interpreted by DFT and TDDFT Calculations
Original language description
X-ray absorption spectra of fac-[ReBr(CO)3(bpy)] near the Re L3- and Br K-edges were measured in a steady-state mode as well as timeresolved at 630 ps after 355 nm laser pulse excitation. Relativistic spinorbit time-dependent density functional theory (TD-DFT) calculations account well for the shape of the near-edge absorption (the "white line") of the ground-state Re spectrum, assigning the lowest-lying transitions as core-toligand metal-to-ligand charge transfer from Re 2p3/2 into predominantly ?*(bpy) molecular orbitals (MOs) containing small 5d contributions, followed in energy by transitions into ?* Re(CO)3 and delocalized ?*/?* MOs. Transitions gain their intensities from Re 5d and 6s participation in the target orbitals. The 5d character is distributed over many unoccupied MOs; the 5d contribution to any single empty MO does not exceed 29%. The Br K-edge spectrum is dominated by the ionization edge and multiple scattering features, the pre-edge electronic transitions being very
Czech name
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Czech description
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Classification
Type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Result continuities
Project
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2013
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
52
Issue of the periodical within the volume
10
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
5775-5785
UT code for WoS article
000319720400025
EID of the result in the Scopus database
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Basic information
Result type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP
CF - Physical chemistry and theoretical chemistry
Year of implementation
2013