Interaction of the NO 3pπ Rydberg state with Ar: Potentialenergy surfaces and spectroscopy

We present the experimental and simulated (2+1) REMPI spectrum of the $\tilde C\,^2 \Pi$C̃Π2 state of the NO–Ar complex, in the vicinity of the3pRydberg state ofNO. Two Rydbergstates of NO are expected in this energy region: theC2Π (3pπ) andD2Σ+ (3pσ) states, and weconcentrate on the former here. Wh...

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Bibliographic Details
Published in:The Journal of chemical physics 2013-06, Vol.138 (21)
Main Authors: Ershova, Olga V, Kłos Jacek, Harris, Joe P, Gardner, Adrian M, Tamé-Reyes, Victor M, Andrejeva, Anna, Besley, Nicholas A, Wright, Timothy G
Format: Article
Language:English
Subjects:
Augmented reality
Mathematical analysis
Potential energy
Spectrum analysis
Wave functions
Online Access:Get full text
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Summary:We present the experimental and simulated (2+1) REMPI spectrum of the $\tilde C\,^2 \Pi$C̃Π2 state of the NO–Ar complex, in the vicinity of the3pRydberg state ofNO. Two Rydbergstates of NO are expected in this energy region: theC2Π (3pπ) andD2Σ+ (3pσ) states, and weconcentrate on the former here. When the C2Π (3pπ) stateinteracts with Ar at nonlinear orientations, the symmetry is lowered toCs, splitting the degeneracy of the 2Π state toyield $\tilde C$C̃(2A″) and $\tilde C$C̃(2A′) states. Forthese two states of NO–Ar, we calculate potential energy surfaces using second order Møller-Plessetperturbation theory, exploiting a procedure to converge the reference Hartree-Fockwavefunction todescribe the excitedstates, the maximum overlap method. The bound rovibrational statesobtained from the surfaces are used to simulate the electronic spectrum, which is inexcellent agreement with experiment, providing assignments for the observed spectral linesfrom the calculated rovibrational wavefunctions.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4808027