1. Ab initio constructed diabatic surfaces of NO2 and the photodetachment spectra of its anion.
- Author
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Mukherjee, Saikat, Mukherjee, Bijit, Sardar, Subhankar, and Adhikari, Satrajit
- Subjects
PHOTODETACHMENT threshold spectroscopy ,NITROGEN oxides ,SURFACE chemistry ,ELECTRONIC structure ,ADIABATIC processes ,POTENTIAL energy surfaces - Abstract
A thorough investigation has been performed for electronic structure, topological effect, and nuclear dynamics of NO
2 molecule, where the adiabatic potential energy surfaces (PESs), conical intersections between the ground (X²A1 ) and the first excited state (A²B2 ), 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 NO2 for performing nuclear dynamics to calculate the photoelectron 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 (X²A1 and A²B2 ) of NO2 is essentially through the asymmetric stretching mode, where the functional form of such interaction is distinctly symmetric and non-linear. [ABSTRACT FROM AUTHOR]- Published
- 2015
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