Ab initio constructed diabatic surfaces of NO{sub 2} and the photodetachment spectra of its anion
Journal Article
·
· Journal of Chemical Physics
- Department of Physical Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032 (India)
A thorough investigation has been performed for electronic structure, topological effect, and nuclear dynamics of NO{sub 2} molecule, where the adiabatic potential energy surfaces (PESs), conical intersections between the ground (X{sup 2}A{sub 1}) and the first excited state (A{sup 2}B{sub 2}), and the corresponding non-adiabatic coupling terms between those states are recalculated [Chem. Phys. 416, 11 (2013)] to achieve enough accuracy in dynamics. We employ beyond Born-Oppenheimer theory for these two state sub-Hilbert space to carry out adiabatic to diabatic transformation (ADT) to obtain the ADT angles and thereby, to construct single-valued, smooth, and continuous diabatic PESs. The analytic expressions for the adiabatic PESs and ADT angles are provided to represent a two-state three-mode diabatic Hamiltonian of NO{sub 2} for performing nuclear dynamics to calculate the photo-electron spectra of its anion. It appears that not only Jahn-Teller type coupling but also Renner-Teller interaction contributes significantly on the overall spectrum. The coupling between the electronic states (X{sup 2}A{sub 1} and A{sup 2}B{sub 2}) of NO{sub 2} is essentially through the asymmetric stretching mode, where the functional form of such interaction is distinctly symmetric and non-linear.
- OSTI ID:
- 22493406
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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