Computational determination of the S1(Ã1Aâ³) absorption spectra of HONO and DONO using full-dimensional neural network potential energy surfaces.
J Chem Phys
; 161(1)2024 Jul 07.
Article
en En
| MEDLINE
| ID: mdl-38953448
ABSTRACT
The Ã1Aâ³ â XÌ1A' absorption spectra of HONO and DONO were simulated by a full six-dimensional quantum mechanical method based on the newly constructed potential energy surfaces for the ground and excited electronic states, which were represented by the neural network method utilizing over 36 000 ab initio energy points calculated at the multireference configuration interaction level with Davidson correction. The absorption spectrum of HONO/DONO comprises a superposition of the spectra from two isomers, namely, trans- and cis-HONO/DONO, due to their coexistence in the ground XÌ1A' state. Our calculated spectra of both HONO and DONO were found to be in fairly good agreement with the experiment, including the energy positions and widths of the peaks. The dominant progression was assigned to the N=O stretch mode (20n) associated with trans-HONO/DONO, which can be attributed to the promotion of an electron to the π* orbital of N=O. Specifically, the resonances with higher vibrational quanta were found to be in the domain of the Feshbach-type resonances. The assignments of the spectra and mode specificity therein are discussed.
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Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
J Chem Phys
Año:
2024
Tipo del documento:
Article
País de afiliación:
China