In most implementations reported in the literature so far, DFT excitations used
for surface hopping are obtained either from linear-response time-dependent theory
or from bare KS gaps. Currently, we observe great effort from different research
groups to generalize the methods for different kinds of nonadiabatic interactions, to
provide better theoretical foundations, and to improve the hopping algorithms. The
availability of SH/DFT in a small amount of public computational-chemistry
software has also helped to popularize the method.
SH/DFT very successfully expanded the range of systems which can be
approached for nonadiabatic dynamics investigations. We should, however, be
aware that many methodological restrictions remain and must still be properly
addressed. Such restrictions involve intrinsic limitations in the semi-classical
local approach for nonadiabatic dynamics, in the sampling of statistical ensembles,
and, more fundamentally, in the quality of the DFT excited-state predictions. In
particular, the multireference character of regions of energy crossing between the
excited and the ground states is still a challenge waiting for better solutions than
those so far available.
Acknowledgments We would like to thank Dr. Michael Filatov for kindly providing the REKS
data for Fig. 3 and also Dr. W. Arbelo-Gonza ´lez, Dr. Fazzi, Dr. G. Rodrigues, and Dr. T. Very for
helpful discussions.
References
1. Winter NOC, Graf NK, Leutwyler S, Hattig C (2013) Phys Chem Chem Phys 15:6623
2. Silva-Junior MR, Thiel W (2010) J Chem Theory Comput 6:1546
3. Silva-Junior MR, Schreiber M, Sauer SPA, Thiel W (2010) J Chem Phys 133:174318
4. Schreiber M, Silva-Junior MR, Sauer SPA, Thiel W (2008) J Chem Phys 128:134110
5. Silva-Junior MR, Schreiber M, Sauer SPA, Thiel W (2008) J Chem Phys 129:104103
6. Wu W, Zhang H, Braı ¨da B, Shaik S, Hiberty P (2014) Theor Chem Acc 133:1
7. Dreuw A, Weisman JL, Head-Gordon M (2003) J Chem Phys 119:2943
8. Yonehara T, Hanasaki K, Takatsuka K (2011) Chem Rev 112:499
9. Yarkony DR (2011) Chem Rev 112:481
10. Worth GA, Cederbaum LS (2004) Annu Rev Phys Chem 55:127
11. Barbatti M (2011) WIREs Comput Mol Sci 1:620
12. Nelson T, Fernandez-Alberti S, Roitberg AE, Tretiak S (2013) J Chem Phys 138:224111
13. Zheng J, Meana-Pan ˜eda R, Truhlar DG (2014) J Phys Chem Lett 5:2039
14. Nelson T, Fernandez-Alberti S, Chernyak V, Roitberg AE, Tretiak S (2012) J Chem Phys
136:054108
15. Akimov AV, Prezhdo OV (2014) Phys Rev Lett 113:153003
16. Gorshkov VN, Tretiak S, Mozyrsky D (2013) Nat Commun 4:2144
17. Kelly A, van Zon R, Schofield J, Kapral R (2012) J Chem Phys 136:084101
18. Nikitin EE (1968) In: Hartmann H, Heidberg J, Heydtmann H, Kohlmaier GH (eds)
Chemische Elementarprozesse. Springer, Berlin
19. Tully JC, Preston RK (1971) J Chem Phys 55:562
20. Curchod BFE, Rothlisberger U, Tavernelli I (2013) ChemPhysChem 14:1314
21. Akimov AV, Neukirch AJ, Prezhdo OV (2013) Chem Rev 113:4496
22. Fabiano E, Keal TW, Thiel W (2008) Chem Phys 349:334
Surface Hopping Dynamics with DFT Excited States
439
for surface hopping are obtained either from linear-response time-dependent theory
or from bare KS gaps. Currently, we observe great effort from different research
groups to generalize the methods for different kinds of nonadiabatic interactions, to
provide better theoretical foundations, and to improve the hopping algorithms. The
availability of SH/DFT in a small amount of public computational-chemistry
software has also helped to popularize the method.
SH/DFT very successfully expanded the range of systems which can be
approached for nonadiabatic dynamics investigations. We should, however, be
aware that many methodological restrictions remain and must still be properly
addressed. Such restrictions involve intrinsic limitations in the semi-classical
local approach for nonadiabatic dynamics, in the sampling of statistical ensembles,
and, more fundamentally, in the quality of the DFT excited-state predictions. In
particular, the multireference character of regions of energy crossing between the
excited and the ground states is still a challenge waiting for better solutions than
those so far available.
Acknowledgments We would like to thank Dr. Michael Filatov for kindly providing the REKS
data for Fig. 3 and also Dr. W. Arbelo-Gonza ´lez, Dr. Fazzi, Dr. G. Rodrigues, and Dr. T. Very for
helpful discussions.
References
1. Winter NOC, Graf NK, Leutwyler S, Hattig C (2013) Phys Chem Chem Phys 15:6623
2. Silva-Junior MR, Thiel W (2010) J Chem Theory Comput 6:1546
3. Silva-Junior MR, Schreiber M, Sauer SPA, Thiel W (2010) J Chem Phys 133:174318
4. Schreiber M, Silva-Junior MR, Sauer SPA, Thiel W (2008) J Chem Phys 128:134110
5. Silva-Junior MR, Schreiber M, Sauer SPA, Thiel W (2008) J Chem Phys 129:104103
6. Wu W, Zhang H, Braı ¨da B, Shaik S, Hiberty P (2014) Theor Chem Acc 133:1
7. Dreuw A, Weisman JL, Head-Gordon M (2003) J Chem Phys 119:2943
8. Yonehara T, Hanasaki K, Takatsuka K (2011) Chem Rev 112:499
9. Yarkony DR (2011) Chem Rev 112:481
10. Worth GA, Cederbaum LS (2004) Annu Rev Phys Chem 55:127
11. Barbatti M (2011) WIREs Comput Mol Sci 1:620
12. Nelson T, Fernandez-Alberti S, Roitberg AE, Tretiak S (2013) J Chem Phys 138:224111
13. Zheng J, Meana-Pan ˜eda R, Truhlar DG (2014) J Phys Chem Lett 5:2039
14. Nelson T, Fernandez-Alberti S, Chernyak V, Roitberg AE, Tretiak S (2012) J Chem Phys
136:054108
15. Akimov AV, Prezhdo OV (2014) Phys Rev Lett 113:153003
16. Gorshkov VN, Tretiak S, Mozyrsky D (2013) Nat Commun 4:2144
17. Kelly A, van Zon R, Schofield J, Kapral R (2012) J Chem Phys 136:084101
18. Nikitin EE (1968) In: Hartmann H, Heidberg J, Heydtmann H, Kohlmaier GH (eds)
Chemische Elementarprozesse. Springer, Berlin
19. Tully JC, Preston RK (1971) J Chem Phys 55:562
20. Curchod BFE, Rothlisberger U, Tavernelli I (2013) ChemPhysChem 14:1314
21. Akimov AV, Neukirch AJ, Prezhdo OV (2013) Chem Rev 113:4496
22. Fabiano E, Keal TW, Thiel W (2008) Chem Phys 349:334
Surface Hopping Dynamics with DFT Excited States
439