February 10, 2022
SHARC-MN - version 1.2
Surface Hopping with Arbitrary Couplings -
MN extension
Yinan Shu
University of Minnesota
Linyao Zhang
Harbin Institute of Technology University of Minnesota
and Donald G. Truhlar
University of Minnesota
SHARC-MN status
Most recent version:
1.2
Date of most recent
version: February 10, 2022
Date of most recent
manual update: February 10, 2022
Introduction to
SHARC-MN
SHARC-MN
is an extended version of SHARC. Both codes are used for direct dynamics
calculations of electronically nonadiabatic processes in which all needed
energies, gradients, and nonadiabatic couplings (NACs) are calculated by
performing electronic structure calculations as they are needed in the dynamics
calculations. SHARC and SHARC-MN include both self-consistent potential (SCP)
and trajectory surface hopping methods. In the former, nuclei are propagated on
a mean-field PES, and in the latter they are propagated on single surface at
any time but can hop between surfaces.
The
following methods are in SHARC-MN but not (at this time) in SHARC:
* SE: semiclassical Ehrenfest [1]
* CSDM: coherent switching with decay of mixing [2,3]
* SCDM: self-consistent decay of mixing [3,4]
* tSE: time-derivative semiclassical Ehrenfest [5]
* tCSDM: time-derivative coherent switching with decay of mixing
[5]
* κSE: curvature-driven semiclassical
Ehrenfest [6]
* κCSDM: curvature-driven coherent switching
with decay of mixing [6]
* κTSH: curvature-driven trajectory surface
hooping [6]
Key features of
SHARC-MN - version 1.2
CSDM,
tCSDM, and κCSDM use a mean-field potential and treat
coherence and decoherence in a balanced way [2,3,6,7]
tCSDM
approximates the nonadiabatic coupling vector (NAC) in terms of effective NAC
derived from time-derivative coupling and can perform nonadiabatic dynamics
without NACs. This is more efficient. [5]
κCSDM approximates the nonadiabatic coupling vector (NAC) in
terms of the curvature of the energy gap and can perform nonadiabatic dynamics
without NACs or time derivatives.
This is not only convenient; it is also very efficient. [6]
Trajectory
surface hopping can also be performed in curvature-driven mode without NACs.
This is called κTSH. [6]
Trajectory
surface hopping and κTSH can be run with energy-based
decoherence corrections [8,2]
All
methods can use projected couplings that conserve the position of the center of
mass and the total nuclear angular momentum. [6,9]
An
adaptive timestep integrator is available. [3]
TSH and κTSH can now perform momentum adjustment and reflection after a frustrated hop on directions of projected NAC, effective NAC, and projected effective NAC.
Additional reading
We
recommend the IJQC paper by Mai et al. [10] for an introduction to the
methods in SHARC.
Users' Manual
The
SHARC-MN-v1.2 User’s Manual is available in PDF form.
Licensing
SHARC-MN-v1.2
is licensed under the GNU general public license
v3.0.
The
manual of SHARC-MN-v1.2 is licensed under CC-BY-4.0.
Publications
of results obtained with SHARC-MN-v1.2 software should cite the program
[11,12].
References
[1]
“What is the Best Semiclassical Method for Photochemical Dynamics in
Systems with Conical Intersections?,” M. S. Topaler, T. C. Allison, D. W.
Schwenke, and D. G. Truhlar, Journal of Chemical Physics 109, 3321-3345 (1998),
110, 687-688(E) (1999), 113, 3928(E) (2000).
doi.org/10.1063/1.477684
[2]
“Coherent Switching with Decay of Mixing: An Improved Treatment of
Electronic Coherence for Non-Born-Oppenheimer Trajectories,” C. Zhu, S. Nangia,
A. W. Jasper, and D. G. Truhlar, Journal of Chemical Physics 121, 7658-7670 (2004).
doi.org/10.1063/1.1793991
[3]
“Implementation of Coherent Switching with Decay of Mixing into the
SHARC Program,” Y. Shu, L. Zhang, S. Mai, S. Sun, L. González, and D. G.
Truhlar, Journal of Chemical Theory and Computation 16, 3464–3475 (2020).
doi.org/10.1021/acs.jctc.0c00112
[4]
“Non-Born-Oppenheimer Trajectories with Self-Consistent Decay of Mixing,
”C. Zhu, A. W. Jasper, and D. G. Truhlar, Journal of Chemical Physics 120,
5543-5557 (2004).
doi.org/10.1063/1.1648306
[5]
“Time-Derivative Couplings for Self-Consistent Electronically
Nonadiabatic Dynamics,” Y. Shu, L. Zhang, S. Sun, and D. G. Truhlar, Journal of
Chemical Theory and Computation 16, 4098-4106 (2020).
doi.org/10.1021/acs.jctc.0c00409
[6]
“Nonadiabatic Dynamics Algorithms with Only Potential Energies and
Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and
Curvature-Driven Trajectory Surface Hopping,” Y. Shu, L. Zhang, S. Sun, Y. Huang,
and D. G. Truhlar, to be published.
Preprint available on ChemRxiv at doi.org/10.33774/chemrxiv-2021-8w6fx
[7]
“Non-Born-Oppenheimer Liouville-von Neumann Dynamics. Evolution of a
Subsystem Controlled by Linear and Population-Driven Decay of Mixing with
Decoherent and Coherent Switching,” C. Zhu, A. W. Jasper, and D. G. Truhlar,
Journal of Chemical Theory and Computation 1, 527-540 (2005).
doi.org/10.1021/ct050021p
[8]
“Critical appraisal of the fewest switches algorithm for surface
hopping,” G. Granucci and M. Persico, Journal of Chemical Physics 126, 134114
(2007).
doi.org/
10.1063/1.2715585
[9]
“Conservation of Angular Momentum in Direct Nonadiabatic Dynamics,” Y.
Shu, L. Zhang, Z. Varga, K. A. Parker, S. Kanchanakungwankul, S. Sun, and D. G.
Truhlar, Journal of Physical Chemistry Letters 11, 1135-1140 (2020).
doi.org/10.1021/acs.jpclett.9b03749
[10] “A General Method to Describe
Intersystem Crossing Dynamics in Trajectory Surface Hopping,” S. Mai, P.
Marquetand, and L. González, International Journal of Quantum Chemistry 115,
1215–1231 (2015).
doi.org/10.1002/qua.24891
[11] Y. Shu, L. Zhang, and D. G. Truhlar,
SHARC-MN-v1.2 (University of Minnesota, Minneapolis, 2022),
https://comp.chem.umn.edu/sharc-mn
[12] S. Mai, M. Richter, M. Heindl, M. F.
S. J. Menger, A. Atkins, M. Ruckenbauer, F. Plasser, L. M. Ibele, S. Kropf, M.
Oppel, P. Marquetand, and L. González, SHARC-v2.1 (University of Vienna, Wien,
2019),
https://sharc-md.org
To obtain
SHARC-MN-v1.2
Downloading
the program affirms agreement with the GNU general public license, Version 3
and the CC-BY-4.0 license and agreement to cite the program.
Acknowledgment
We
requested permission from the authors of SHARC-v2.1 to distribute this modified
version of the code, and we were given permission. We are grateful to the
authors of SHARC-v2.1 for making their code available and for their cooperation
every step of the way.
Our
work on the MN extension of SHARC-v2.1 was supported in part by the U. S.
Department of Energy, Office of Basic Energy Sciences.
Links to other pages
of interest
Donald G. Truhlar's Software Page
Computational Chemistry at the University
of Minnesota
Minnesota Supercomputing Institute
Department of Chemistry at the University of
Minnesota
This document was last modified on February
11, 2022.
Updated by: Software Manager