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How to Interpret Trajectory Surface Hopping Dynamics?

Tomislav Piteša�Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, Croatia

tpitesa@irb.hr

Computational Chemistry Day 2022

24 Sept 2022, IRB, Zagreb, Croatia

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Born-Oppenheimer Molecular Dynamics

  • Classical Molecular Dynamics

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  • Quantum Molecular Dynamics

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Potential energy surface

 

+THERMOSTAT

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Photoinduced reactions

BO approximation

 

 

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Nonadiabatic Molecular Dynamics

 

 

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Trajectory Surface Hopping Dynamics

  • John Tully (1990): Fewest Switches Surface Hopping (FSSH) Dynamics:

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Mixed Quantum-Classical Nonadiabatic Dynamics

Classical nonadiabatic�nuclear motion

Qauntum nonadiabatic �electronic motion

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Trajectory Surface Hopping Dynamics

 

 

 

 

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Pyrazine photodynamics

 

 

 

T. Piteša et al, J. Chem. Theory Comput. 17 (2021) 5098-5109.

 

 

 

 

 

6ag(n)

1b1g(π)

2b3u(π*)

1au(π*)

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Pyrazine photodynamics

 

 

 

T. Piteša et al, J. Chem. Theory Comput. 17 (2021) 5098-5109.

 

 

 

 

 

6ag(n)

1b1g(π)

2b3u(π*)

1au(π*)

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A single trajectory…

 

 

 

 

 

 

 

 

 

 

 

 

 

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Configurationally uniform states

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A single trajectory…

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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Taken from: T. Horio et al. J. Chem. Phys. 145 (2016) 044306.

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  • Trajectory Surface Hopping Dynamics:
    • Classical Nuclear + Quantum Electronic + Nonadiabatic Dynamics
    • One does not immediatelly see the physically meaningful picture of the simulated process (due to the usage of electronic eigenstates)
    • Automatized generation of configurationally uniform states along nonadiabatic trajectories

Summary

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Thank you for your kind attention!

Dr. Nađa Došlić

Dr. Marin Sapunar

Prof. Wolfgang Domcke

Croatian Science Fundation

Research Group Linkage �Programme