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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Real space atomic decomposition of fundamental properties of carbon monoxide in the ground and the two lowest lying excited electronic states

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Autor(es):
Terrabuio, Luiz Alberto ; da Silva, Natieli Alves ; Andrade Haiduke, Roberto Luiz ; Matta, Cherif F.
Número total de Autores: 4
Tipo de documento: Artigo Científico
Fonte: Molecular Physics; v. 115, n. 15-16, SI, p. 1955-1965, 2017.
Citações Web of Science: 3
Resumo

The properties of carbon monoxide in its ground and two lowest lying excited states are investigated by conventional and time-dependent (TD) density functional theory (DFT). The dipole moment is decomposed into atomic polarisation (AP) and inter-atomic charge transfer (CT) contributions according to the quantum theory of atoms in molecules (QTAIM). Considerable AP and CT contributions cancel in the ground state (S-0) resulting in its known negligible dipole moment. This balance is disturbed in the lowest triplet (T-1) and singlet (S-1) excited states, resulting in dipole moments of 1.57 D for T-1 and 0.49 D for S-1. The AP decreases by 2.5 D on excitation to either state but the opposing CT is reduced by 0.8 D for T-1 and by 1.8 D for S-1, insufficient for cancellation. These excitations induce charge transfer from O to C which drives dipole changes accompanied by a weakening of the C-O bond, more pronounced in the S-1 state, as trends in bond lengths, vibrational frequencies, and QTAIM properties suggest. The charge-charge flux-dipole flux (CCFDF) model in terms of QTAIM parameters reveals that the vibrational stretching band weakening on excitation is predominantly due to changes in atomic charges. {[}GRAPHICS] . (AU)

Processo FAPESP: 14/23714-1 - Cálculos relativísticos de estrutura eletrônica para avaliação de novos conjuntos de funções de base sem prolapso variacional
Beneficiário:Roberto Luiz Andrade Haiduke
Linha de fomento: Auxílio à Pesquisa - Regular
Processo FAPESP: 10/18743-1 - Uso de multipolos da teoria quântica de átomos em moléculas e estudos cinéticos em sistemas encontrados no meio interestelar
Beneficiário:Roberto Luiz Andrade Haiduke
Linha de fomento: Auxílio à Pesquisa - Regular