The electronic excited states of ethylene with large-amplitude deformations: A dynamical symmetry group investigation

被引：25

作者：

Lasorne, B. ^{[1
]}

Robb, Michael A. ^{[2
]}

Meyer, Hans-Dieter ^{[3
]}

Gatti, F. ^{[1
]}

机构：

[1] Univ Montpellier 2, CTMM, UMR CNRS UM2 ENSCM UM1 5253, Inst Charles Gerhardt Montpellier, F-34095 Montpellier, France

[2] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AZ, England

[3] Univ Heidelberg, Inst Phys Chem, D-69120 Heidelberg, Germany

来源：

CHEMICAL PHYSICS | 2010年 / 377卷 / 1-3期

关键词：

Ethylene; Ethene; Photochemistry; Diabatization; Vibronic model; Excited electronic states; Large-amplitude deformations; Curvilinear coordinates; Dynamical symmetry; Complete nuclear-permutation-inversion group; CONICAL INTERSECTIONS; VACUUM-ULTRAVIOLET; PHOTOINDUCED DYNAMICS; NONADIABATIC DYNAMICS; ENERGY SURFACES; VALENCE STATES; WAVE-FUNCTIONS; AB-INITIO; ETHENE; SPECTRUM;

D O I：

10.1016/j.chemphys.2010.08.011

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：

We show that the lowest manifold of electronic states of ethylene (ethene, C(2)H(4)) can be described correctly with a complete active space of 17 quasidiabatic configurations built on state-averaged orbitals. This space is stable upon large-amplitude deformations, such as torsion, pyramidalization, CC stretching and HCH bending. The properties of the nuclear coordinates and valence and Rydberg electronic states are investigated within the framework of nuclear-permutation-inversion group theory. This systematic analysis is compared to a previous model of the valence states of ethylene (R. P. Krawczyk, A. Viel, U. Manthe, W. Domcke, J. Chem. Phys. 119 (2003) 1397). Our approach is intended to be generalized to the non-adiabatic photochemistry of organic molecules where large-amplitude deformations require global vibronic Hamiltonian models to be expressed in terms of simple functions of polyspherical valence coordinates. (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：30 / 45

页数：16

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