The Character of Low-Lying Excited States of Mixed-Ligand Metal Carbonyls. TD-DFT and CASSCF/CASPT2 Study of [W(CO)4L] (L = ethylenediamine, N, N'-di-alkyl-1,4-diazabutadiene) and [W(CO)5L] (L = pyridine, 4-cyanopyridine).
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030026" target="_blank" >RIV/61388955:_____/03:54030026 - isvavai.cz</a>
Result on the web
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DOI - Digital Object Identifier
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Alternative languages
Result language
angličtina
Original language name
The Character of Low-Lying Excited States of Mixed-Ligand Metal Carbonyls. TD-DFT and CASSCF/CASPT2 Study of [W(CO)4L] (L = ethylenediamine, N, N'-di-alkyl-1,4-diazabutadiene) and [W(CO)5L] (L = pyridine, 4-cyanopyridine).
Original language description
This contribution presents the results of the TD-DFT and CASSCF/CASPT2 calculations on [W(CO)4(MeDAB)] (MeDAB=N,N''-di-methyl-1,4-diazabutadiene), [W(CO)4(en)] (en = ethylenediamine), [W(CO)5(py)] (py=pyridine) and [W(CO)5(CNpy)] (CNpy=4-cyanopyridine) complexes. Contrary to the textbook interpretation, calculations on the model complex [W(CO)4(MeDAB)] and [W(CO)5(CNpy)] show that the lowest W MeDAB and WCNpy MLCT excited states are immediately followed in energy by several WCO MLCT states, instead of LF states. The lowest lying excited states of [W(CO)4(en)] system were characterized as W(COeq)2COax CT excitations, which involve a remarkable electron density redistribution between axial and equatorial CO ligands. [W(CO)5(py)] possesses closely lying WCO and Wpy MLCT excited states. The calculated energies of these states are sensitive to the computational methodology used and can be easily influenced by a substitution effect.
Czech name
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Czech description
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Classification
Type
J<sub>x</sub> - 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
<a href="/en/project/OC%20D14.20" target="_blank" >OC D14.20: Oganometallic and Metallo-organic Building Blocks for Photonic Materials</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2003
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Collection of Czechoslovak Chemical Communications
ISSN
0010-0765
e-ISSN
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Volume of the periodical
68
Issue of the periodical within the volume
1
Country of publishing house
CZ - CZECH REPUBLIC
Number of pages
16
Pages from-to
89-104
UT code for WoS article
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EID of the result in the Scopus database
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