Top Curr Chem (2016) 368: 415–444
DOI: 10.1007/128_2014_605
# Springer International Publishing Switzerland 2014
Published online: 24 February 2015
Surface Hopping Dynamics with DFT
Excited States
Mario Barbatti and Rachel Crespo-Otero
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
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
2 Surface Hopping Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
3 Excited States in DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
3.1 Excitation Energies in DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
3.2 Nonadiabatic Couplings in DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
3.3 Critical Appraisal . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . . . .. . . . . . . . 428
M. Barbatti (*)
Max-Planck-Institut fu ¨r Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mu ¨lheim an der
Ruhr, Germany
e-mail: barbatti@kofo.mpg.de
R. Crespo-Otero
School of Biological and Chemical Sciences, Queen Mary University of London, Mile End
Road, London E1 4NS, UK
DOI: 10.1007/128_2014_605
# Springer International Publishing Switzerland 2014
Published online: 24 February 2015
Surface Hopping Dynamics with DFT
Excited States
Mario Barbatti and Rachel Crespo-Otero
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
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
2 Surface Hopping Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
3 Excited States in DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
3.1 Excitation Energies in DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
3.2 Nonadiabatic Couplings in DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
3.3 Critical Appraisal . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . . . .. . . . . . . . 428
M. Barbatti (*)
Max-Planck-Institut fu ¨r Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mu ¨lheim an der
Ruhr, Germany
e-mail: barbatti@kofo.mpg.de
R. Crespo-Otero
School of Biological and Chemical Sciences, Queen Mary University of London, Mile End
Road, London E1 4NS, UK