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.

     Download manual.

 

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‚Äì3475 (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.

     Download SHARC-MN-v1.2

 

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 Home Page

Donald G. Truhlar's Software Page

Computational Chemistry at the University of Minnesota

Minnesota Supercomputing Institute

Department of Chemistry at the University of Minnesota

SHARC Home Page

 

 

This document was last modified on February 11, 2022.

Updated by: Software Manager