Non-Born-Oppenheimer path in anti-Hermitian dynamics for nonadiabatic transitions
- Department of Basic Science, The University of Tokyo, Komaba, 153-8902 Tokyo (Japan)
A serious difficulty in the semiclassical Ehrenfest theory for nonadiabatic transitions is that a path passing across the avoided crossing is forced to run on a potential averaged over comprising adiabatic potential surfaces that commit the avoided crossing. Therefore once a path passes through the crossing region, it immediately becomes incompatible with the standard view of 'classical trajectory' running on an adiabatic surface. This casts a fundamental question to the theoretical structure of chemical dynamics. In this paper, we propose a non-Born-Oppenheimer path that is generated by an anti-Hermitian Hamiltonian, whose complex-valued eigenenergies can cross in their real parts and avoid crossing in the imaginary parts in the vicinity of the nonadiabatic transition region. We discuss the properties of this non-Born-Oppenheimer path and thereby show its compatibility with the Born-Oppenheimer classical trajectories. This theory not only allows the geometrical branching of the paths but gives the nonadiabatic transition amplitudes and quantum phases along the generated paths.
- OSTI ID:
- 20783224
- Journal Information:
- Journal of Chemical Physics, Vol. 124, Issue 6; Other Information: DOI: 10.1063/1.2167648; (c) 2006 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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