Abstract
Nonadiabatic dynamics simulation of electronically-excited states has been a research area of fundamental importance, providing support for spectroscopy, explaining photoinduced processes, and predicting new phenomena in a variety of specialties, from basic physical-chemistry, through molecular biology, to materials engineering. The demands in the field, however, are quickly growing, and the development of surface hopping based on density functional theory (SH/DFT) has been a major advance in the field. In this contribution, the surface hopping approach, the methods for computation of excited states based on DFT, the connection between these methodologies, and their diverse implementations are reviewed. The shortcomings of the methods are critically addressed and a number of case studies from diverse fields are surveyed.
Keywords
- Density functional theory
- Excited states
- Nonadiabatic dynamics
- Photochemistry
- Surface hopping
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Abbreviations
- ADC:
-
Algebraic diagrammatic construction
- ALDA:
-
Adiabatic local density approximation
- CASSCF:
-
Complete active space self-consistent field
- CC:
-
Coupled cluster
- CI:
-
Configuration interaction
- CIS:
-
CI with single excitations
- CPA:
-
Classical path approximation
- DFT:
-
Density functional theory
- DFTB:
-
Density functional based tight binding
- DISH:
-
Decoherence-induced surface hopping
- GFSH:
-
Global-flux surface hopping
- LR:
-
Linear response
- KS:
-
Kohn–Sham
- MCSCF:
-
Multiconfigurational self-consistent field
- MRCI:
-
Multireference CI
- MR-CISD:
-
MRCI with singles and doubles
- MRPT:
-
Multireference perturbation theory
- REKS:
-
Spin-restricted ensemble-referenced KS
- ROKS:
-
Restricted open-shell KS
- RPA:
-
Random phase approximation
- SDKS:
-
Single determinant KS
- SH:
-
Surface hopping
- SH/DFT:
-
Surface hopping with DFT excited states
- TD:
-
Time-dependent
- TDA:
-
Tamm–Dancoff approximation
- TDHF:
-
Time-dependent Hartree–Fock
- UBS:
-
Spin-unrestricted broken symmetry
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Acknowledgments
We would like to thank Dr. Michael Filatov for kindly providing the REKS data for Fig. 3 and also Dr. W. Arbelo-González, Dr. Fazzi, Dr. G. Rodrigues, and Dr. T. Very for helpful discussions.
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Barbatti, M., Crespo-Otero, R. (2014). Surface Hopping Dynamics with DFT Excited States. In: Ferré, N., Filatov, M., Huix-Rotllant, M. (eds) Density-Functional Methods for Excited States. Topics in Current Chemistry, vol 368. Springer, Cham. https://doi.org/10.1007/128_2014_605
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