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N-3(+): Full-dimensional ground state potential energy surface, vibrational energy levels, and dynamics

Koner, Debasish and Schwilk, Max and Patra, Sarbani and Bieske, Evan J. and Meuwly, Markus. (2020) N-3(+): Full-dimensional ground state potential energy surface, vibrational energy levels, and dynamics. JOURNAL OF CHEMICAL PHYSICS, 153 (4). 044302.

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Official URL: https://edoc.unibas.ch/80558/

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Abstract

The fundamental vibrational frequencies and higher vibrationally excited states for the N3+ ion in its electronic ground state have been determined from quantum bound state calculations on three-dimensional potential energy surfaces (PESs) computed at the coupled-cluster singles and doubles with perturbative triples [CCSD(T)]-F12b/aug-cc-pVTZ-f12 and multireference configuration interaction singles and doubles with quadruples (MRCISD+Q)/aug-cc-pVTZ levels of theory. The vibrational fundamental frequencies are 1130 cm(-1) (nu(1), symmetric stretch), 807 cm(-1) (nu(3), asymmetric stretch), and 406 cm(-1) (nu(2), bend) on the higher-quality CCSD(T)-F12b surface. Bound state calculations based on even higher level PESs [CCSD(T)-F12b/aug-cc-pVQZ-f12 and MRCISD+Q-F12b/aug-cc-pVTZ-f12] confirm the symmetric stretch fundamental frequency as similar to 1130 cm(-1). This compares with an estimated frequency from experiment at 1170 cm(-1) and previous calculations [Chambaud et al., Chem. Phys. Lett. 231, 9-12 (1994)] at 1190 cm(-1). The remaining disagreement with the experimental frequency is attributed to uncertainties associated with the widths and positions of the experimental photoelectron peaks. Analysis of the reference complete active space self-consistent field wave function for the MRCISD+Q calculations provides deeper insight into the shape of the PES and lends support for the reliability of the Hartree-Fock reference wave function for the coupled cluster calculations. According to this, N-3(+) has a mainly single reference character in all low-energy regions of its electronic ground state ((3)A '') PES.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Meuwly, Markus
Item Type:Article, refereed
Article Subtype:Research Article
ISSN:0021-9606
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:16 Mar 2021 10:52
Deposited On:16 Mar 2021 10:52

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