Journal
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Volume 109, Issue 4, Pages 650-667Publisher
WILEY
DOI: 10.1002/qua.21870
Keywords
Born-Oppenheimer treatment; Non-adiabatic coupling elements; ADT; Curl-Divergence equation; extended Born-Oppenheimer equation
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Funding
- Department of Science and Technology (DST, Government of India) [SP/S1/H-53/01]
- UGC, Government of India through DSA-SAP-III
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If a coupled three-state electronic manifold forms a sub-Hilbert space, it is possible to express the non-adiabatic coupling (NAC) elements in terms of adiabatic-diabatic transformation (ADT) angles. Consequently, we demonstrate: (a) Those explicit forms of the NAC terms satisfy the Curl conditions with non-zero Divergences; (b) The formulation of extended Born-Oppenheimer (EBO) equation for any three-state BO system is possible only when there exists coordinate independent ratio of the gradients for each pair of ADT angles leading to zero Curls at and around the conical intersection(s). With these analytic advancements, we formulate a rigorous EBO equation and explore its validity as well as necessity with respect to the approximate one (Sarkar and Adhikari, j Chem phys 2006, 124, 074101) by performing numerical calculations on two different models constructed with different chosen forms of the NAC elements. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 109: 650-667, 2009
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