TY - JOUR
T1 - Nonadiabatic Dynamics Algorithms with only Potential Energies and Gradients
T2 - Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping
AU - Shu, Yinan
AU - Zhang, Linyao
AU - Chen, Xiye
AU - Sun, Shaozeng
AU - Huang, Yudong
AU - Truhlar, Donald G.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/3/8
Y1 - 2022/3/8
N2 - Direct dynamics by mixed quantum-classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic structure theory. For example, at every time step of a trajectory, nonadiabatic dynamics requires potential energy surfaces, their gradients, and the matrix elements coupling the surfaces. The need for the couplings can be alleviated by employing the time derivatives of the wave functions, which can be evaluated from overlaps of electronic wave functions at successive time steps. However, evaluation of overlap integrals is still expensive for large systems. In addition, for electronic structure methods for which the wave functions or the coupling matrix elements are not available, nonadiabatic dynamics algorithms become inapplicable. In this work, building on recent work by Baeck and An, we propose new nonadiabatic dynamics algorithms that only require adiabatic potential energies and their gradients. The new methods are named curvature-driven coherent switching with decay of mixing (κCSDM) and curvature-driven trajectory surface hopping (κTSH). We show how powerful these new methods are in terms of computation time and accuracy as compared to previous mixed quantum-classical nonadiabatic dynamics algorithms. The lowering of the computational cost will allow longer nonadiabatic trajectories and greater ensemble averaging to be affordable, and the ability to calculate the dynamics without electronic structure coupling matrix elements extends the dynamics capability to new classes of electronic structure methods.
AB - Direct dynamics by mixed quantum-classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic structure theory. For example, at every time step of a trajectory, nonadiabatic dynamics requires potential energy surfaces, their gradients, and the matrix elements coupling the surfaces. The need for the couplings can be alleviated by employing the time derivatives of the wave functions, which can be evaluated from overlaps of electronic wave functions at successive time steps. However, evaluation of overlap integrals is still expensive for large systems. In addition, for electronic structure methods for which the wave functions or the coupling matrix elements are not available, nonadiabatic dynamics algorithms become inapplicable. In this work, building on recent work by Baeck and An, we propose new nonadiabatic dynamics algorithms that only require adiabatic potential energies and their gradients. The new methods are named curvature-driven coherent switching with decay of mixing (κCSDM) and curvature-driven trajectory surface hopping (κTSH). We show how powerful these new methods are in terms of computation time and accuracy as compared to previous mixed quantum-classical nonadiabatic dynamics algorithms. The lowering of the computational cost will allow longer nonadiabatic trajectories and greater ensemble averaging to be affordable, and the ability to calculate the dynamics without electronic structure coupling matrix elements extends the dynamics capability to new classes of electronic structure methods.
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U2 - 10.1021/acs.jctc.1c01080
DO - 10.1021/acs.jctc.1c01080
M3 - Article
C2 - 35104136
AN - SCOPUS:85124283526
SN - 1549-9618
VL - 18
SP - 1320
EP - 1328
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 3
ER -