Nonadiabatic couplings from the Kohn-Sham derivative matrix: Formulation by time-dependent density-functional theory and evaluation in the pseudopotential framework

Journal Article · Wed Dec 15 00:00:00 EST 2010 · Physical Review. A

DOI:https://doi.org/10.1103/PHYSREVA.82.062508· OSTI ID:21528867

Hu, Chunping ^[1]; Sugino, Osamu; Hirai, Hirotoshi ^[2]; Tateyama, Yoshitaka ^[1]

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1. WPI International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044 (Japan)
2. Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba 277-8581 (Japan)

We study the time-dependent density-functional theory formulation of nonadiabatic couplings (NAC's) to settle problems regarding practical calculations. NAC's have so far been rigorously formulated on the basis of the density response scheme and expressed using the nuclear derivative of the Hamiltonian, {partial_derivative}H/{partial_derivative}R, whereby causing the pseudopotential problem. When rewritten using the nuclear derivative operator, {partial_derivative}/{partial_derivative}R, or the d operator, the formula is found free of the problem and thus provides a working numerical scheme. The d-operator-based formulation also allows us to lay a foundation on the empirical Slater transition-state method and to show an improved way of using the auxiliary excited-state wave-function ansatz, both of which have been utilized in previous works. Evaluation of NAC near either the Jahn-Teller or the Renner-Teller intersection in various molecular systems shows that the values of NAC are much improved over previous calculations when the d-operator formula is implemented in the pseudopotential framework.

• OSTI ID: 21528867
• Journal Information: Physical Review. A, Vol. 82, Issue 6; Other Information: DOI: 10.1103/PhysRevA.82.062508; (c) 2010 American Institute of Physics; ISSN 1050-2947
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
COUPLINGS
DENSITY FUNCTIONAL METHOD
EVALUATION
HAMILTONIANS
JAHN-TELLER EFFECT
MATHEMATICAL OPERATORS
MATRICES
POTENTIALS
TIME DEPENDENCE
WAVE FUNCTIONS
CALCULATION METHODS
FUNCTIONS
QUANTUM OPERATORS
VARIATIONAL METHODS