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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

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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Terrabuio, Luiz Alberto ; da Silva, Natieli Alves ; Andrade Haiduke, Roberto Luiz ; Matta, Cherif F.
Total Authors: 4
Document type: Journal article
Source: Molecular Physics; v. 115, n. 15-16, SI, p. 1955-1965, 2017.
Web of Science Citations: 3

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)

FAPESP's process: 14/23714-1 - Electronic structure relativistic calculations for evaluation of new prolapse-free basis sets
Grantee:Roberto Luiz Andrade Haiduke
Support type: Regular Research Grants
FAPESP's process: 10/18743-1 - Employment of multipoles from the quantum theory of atoms in molecules and kinetic studies in systems found in the interstellar medium
Grantee:Roberto Luiz Andrade Haiduke
Support type: Regular Research Grants