Towards a higher-order description of Jahn-Teller coupling effects in molecular spectroscopy:: The (A)over-tilde2E" state of NO3

被引：56

作者：

Faraji, Shirin ^{[1
]}

Koeppel, Horst ^{[1
]}

Eisfeld, Wolfgang ^{[2
]}

Mahapatra, Susanta ^{[3
]}

机构：

[1] Heidelberg Univ, Inst Phys Chem, INF 229, D-69120 Heidelberg, Germany

[2] Univ Bielefeld, D-33615 Bielefeld, Germany

[3] PO Cent Univ, Univ Hyderabad, Sch Chem, Hyderabad 500046, Andhra Pradesh, India

来源：

CHEMICAL PHYSICS | 2008年 / 347卷 / 1-3期

关键词：

Jahh-Teller effect; NO3; radical; vibronic coupling; photodetachment spectrum;

D O I：

10.1016/j.chemphys.2007.10.006

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Static and dynamic Jahn-Teller coupling effects in the E-2" excited electronic state of the nitrate radical (NO3) are analyzed theoretically. An earlier vibronic coupling model proposed by us [S. Mahapatra, W. Eisfeld, H. Koppel, Chem. Phys. Lett. 441 (2007) 7] is extended here and the importance of higher-order coupling terms established. More specifically, the earlier analysis rests on a quadratic-coupling approach where terms up to second order in the nuclear displacements are retained. In the present analysis we find coupling terms of 3rd and 4th order to be important. This is related to low-energy dissociation thresholds in the system which render the (diabatic) potential energy surfaces anharmonic already for low excitation energies. The results are compared with the experimental photodetachment spectrum of Neumark and coworkers [A. Weaver, D.W. Arnold, S.E. Bradforth, D.M. Neumark, J. Chem. Phys. 94 (1991) 1740], and the agreement is much improved when the additional coupling terms are taken into account. (c) 2007 Elsevier B.V. All rights reserved.

引用

页码：110 / 119

页数：10

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