| Full text | |
| Author(s): |
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, p. 11-pg., 2017-01-01. |
| Abstract | |
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 Opportunities: | 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 Opportunities: | Regular Research Grants |