Practical methods for simulating photo-induced dynamics of molecules often rely on a trajectory-description of the nuclear dynamics, incorporating approximate electron-nuclear feedback. Through approximating electron–nuclear correlation terms in the exact factorization approach, trajectory-based methods have been derived and successfully applied to the dynamics of a variety of light-induced molecular processes, capturing quantum (de)coherence effects rigorously. These terms account for the coupling among the trajectories, recovering the nonlocal nature of quantum nuclear dynamics that is completely overlooked in traditional independent-trajectory algorithms. Nevertheless, some of the approximations introduced in the derivation of some of these methods do not conserve the total energy. We analyze energy conservation in the coupled trajectory mixed quantum-classical (CTMQC) algorithm and explore the performance of a modified algorithm, CTMQC-E, where some of the terms are redefined to restore energy conservation. Here, a set of molecular models is used as a test, namely, 2-cis-penta-2,4-dienimium cation, bis(methylene) adamantyl radical cation, butatriene cation, uracil radical cation, and neutral pyrazine.
Arribas, Evaristo Villaseco, et al. "Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics." Journal of Chemical Theory and Computation, vol. 19, no. 21, Oct. 2023. https://doi.org/10.1021/acs.jctc.3c00845
Arribas, Evaristo Villaseco, Ibele, Lea M., Lauvergnat, David, Maitra, Neepa T., & Agostini, Federica (2023). Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics. Journal of Chemical Theory and Computation, 19(21). https://doi.org/10.1021/acs.jctc.3c00845
Arribas, Evaristo Villaseco, Ibele, Lea M., Lauvergnat, David, et al., "Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics," Journal of Chemical Theory and Computation 19, no. 21 (2023), https://doi.org/10.1021/acs.jctc.3c00845
@article{osti_2530500,
author = {Arribas, Evaristo Villaseco and Ibele, Lea M. and Lauvergnat, David and Maitra, Neepa T. and Agostini, Federica},
title = {Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics},
annote = {Practical methods for simulating photo-induced dynamics of molecules often rely on a trajectory-description of the nuclear dynamics, incorporating approximate electron-nuclear feedback. Through approximating electron–nuclear correlation terms in the exact factorization approach, trajectory-based methods have been derived and successfully applied to the dynamics of a variety of light-induced molecular processes, capturing quantum (de)coherence effects rigorously. These terms account for the coupling among the trajectories, recovering the nonlocal nature of quantum nuclear dynamics that is completely overlooked in traditional independent-trajectory algorithms. Nevertheless, some of the approximations introduced in the derivation of some of these methods do not conserve the total energy. We analyze energy conservation in the coupled trajectory mixed quantum-classical (CTMQC) algorithm and explore the performance of a modified algorithm, CTMQC-E, where some of the terms are redefined to restore energy conservation. Here, a set of molecular models is used as a test, namely, 2-cis-penta-2,4-dienimium cation, bis(methylene) adamantyl radical cation, butatriene cation, uracil radical cation, and neutral pyrazine.},
doi = {10.1021/acs.jctc.3c00845},
url = {https://www.osti.gov/biblio/2530500},
journal = {Journal of Chemical Theory and Computation},
issn = {ISSN 1549-9618},
number = {21},
volume = {19},
place = {United States},
publisher = {American Chemical Society},
year = {2023},
month = {10}}
ANR Q-DeLight; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0019394; SC0020044
OSTI ID:
2530500
Alternate ID(s):
OSTI ID: 2998481
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 21 Vol. 19; ISSN 1549-9618
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011https://doi.org/10.1098/rsta.2013.0059