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  Metal-to-metal charge-transfer transitions: reliable excitation energies from ab initio calculations

Domingo, A., Àngels Carvajal, M., de Graaf, C., Sivalingam, K., Neese, F., & Angeli, C. (2012). Metal-to-metal charge-transfer transitions: reliable excitation energies from ab initio calculations. Theoretical Chemistry Accounts, 131(9): 1264. doi:10.1007/s00214-012-1264-1.

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 Creators:
Domingo, Alex1, 2, Author
Àngels Carvajal, Maria1, Author
de Graaf, Coen1, 3, Author
Sivalingam, Kantharuban4, Author              
Neese, Frank4, Author              
Angeli, Celestino5, Author
Affiliations:
1Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007, Tarragona, Spain, ou_persistent22              
2Laboratoire de Chimie Quantique, Institut de Chimie UMR 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67000, Strasbourg, France, ou_persistent22              
3Institució Catalana de Recerca i Estudis Avançats (ICREA), Passeig Lluís Companys 23, 08010, Barcelona, Spain, ou_persistent22              
4Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023879              
5Dipartimento di Chimica, Università di Ferrara, via Borsari 46, 44121, Ferrara, Italy, ou_persistent22              

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Free keywords: Metal-to-metal charge transfer; Photomagnetism; CASPT2; NEVPT2; TD-DFT
 Abstract: A computational strategy is presented to describe excited states, involving the transfer of an electron from one metallic site to a neighboring metal center, the so-called metal-to-metal charge-transfer (MMCT) states. An accurate ab initio treatment of these states in transition metal compounds is intrinsically difficult for both time-dependent density functional and wave function-based methods. The rather large dependence of the MMCT energies on the applied functional makes difficult to extract reliable estimates from density functional theory, while the standard multiconfigurational approach (complete active space SCF + second-order perturbation theory) leads to severe intruder state problems and unrealistic, negative energies. The analysis of the failure of the multiconfigurational approach shows that the state-average orbitals are biased toward the ground state and strongly deficient to describe the MMCT state. We propose a method to improve the orbitals by gradually approaching as much as possible the state-specific description of the MMCT state in the reference wave function for the second-order perturbation treatment of the dynamic electron correlation.

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Language(s): eng - English
 Dates: 2012-05-162012-08-192012-09-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1007/s00214-012-1264-1
 Degree: -

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Title: Theoretical Chemistry Accounts
  Abbreviation : Theor. Chem. Acc.
Source Genre: Journal
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Publ. Info: Heidelberg : Springer-Verlag
Pages: - Volume / Issue: 131 (9) Sequence Number: 1264 Start / End Page: - Identifier: ISSN: 1432-881X
CoNE: https://pure.mpg.de/cone/journals/resource/954925623262