期刊
JOURNAL OF CHEMICAL PHYSICS
卷 142, 期 6, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4906941
关键词
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资金
- NSF [CHE-1150851]
- Department of Energy [DE-SC0008694]
- Cottrell Research Scholar Fellowship
- David and Lucile Packard Fellowship
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1150851] Funding Source: National Science Foundation
- U.S. Department of Energy (DOE) [DE-SC0008694] Funding Source: U.S. Department of Energy (DOE)
We present a complete derivation of derivative couplings between excited states in the framework of adiabatic time-dependent density functional response theory. Explicit working equations are given and the resulting derivative couplings are compared with derivative couplings from a pseudo-wavefunction ansatz. For degenerate excited states, i.e., close to a conical intersection (CI), the two approaches are identical apart from an antisymmetric overlap term. However, if the difference between two excitation energies equals another excitation energy, the couplings from response theory exhibit an unphysical divergence. This spurious behavior is a result of the adiabatic or static kernel approximation of time-dependent density functional theory leading to an incorrect analytical structure of the quadratic response function. Numerical examples for couplings close to a CI and for well-separated electronic states are given. (C) 2015 AIP Publishing LLC.
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