Kyungpook National Univ., Daegu (Korea, Republic of)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States)
Conical intersections control excited state reactivity, and thus, elucidating and predicting their geometric and energetic characteristics are crucial for understanding photochemistry. Locating these intersections requires accurate and efficient electronic structure methods. Unfortunately, the most accurate methods (e.g., multireference perturbation theories such as XMS-CASPT2) are computationally challenging for large molecules. The state-interaction state-averaged restricted ensemble referenced Kohn–Sham (SI-SA-REKS) method is a computationally efficient alternative. The application of SI-SA-REKS to photochemistry was previously hampered by a lack of analytical nuclear gradients and nonadiabatic coupling matrix elements. We have recently derived analytical energy derivatives for the SI-SA-REKS method and implemented the method effectively on graphical processing units. We demonstrate that our implementation gives the correct conical intersection topography and energetics for several examples. Furthermore, our implementation of SI-SA-REKS is computationally efficient, with observed sub-quadratic scaling as a function of molecular size. This demonstrates the promise of SI-SA-REKS for excited state dynamics of large molecular systems.
Liu, Fang, et al. "Analytical derivatives of the individual state energies in ensemble density functional theory. II. Implementation on graphical processing units (GPUs)." Journal of Chemical Physics, vol. 154, no. 10, Mar. 2021. https://doi.org/10.1063/5.0041389
Liu, Fang, Filatov, Michael, & Martínez, Todd J. (2021). Analytical derivatives of the individual state energies in ensemble density functional theory. II. Implementation on graphical processing units (GPUs). Journal of Chemical Physics, 154(10). https://doi.org/10.1063/5.0041389
Liu, Fang, Filatov, Michael, and Martínez, Todd J., "Analytical derivatives of the individual state energies in ensemble density functional theory. II. Implementation on graphical processing units (GPUs)," Journal of Chemical Physics 154, no. 10 (2021), https://doi.org/10.1063/5.0041389
@article{osti_1776568,
author = {Liu, Fang and Filatov, Michael and Martínez, Todd J.},
title = {Analytical derivatives of the individual state energies in ensemble density functional theory. II. Implementation on graphical processing units (GPUs)},
annote = {Conical intersections control excited state reactivity, and thus, elucidating and predicting their geometric and energetic characteristics are crucial for understanding photochemistry. Locating these intersections requires accurate and efficient electronic structure methods. Unfortunately, the most accurate methods (e.g., multireference perturbation theories such as XMS-CASPT2) are computationally challenging for large molecules. The state-interaction state-averaged restricted ensemble referenced Kohn–Sham (SI-SA-REKS) method is a computationally efficient alternative. The application of SI-SA-REKS to photochemistry was previously hampered by a lack of analytical nuclear gradients and nonadiabatic coupling matrix elements. We have recently derived analytical energy derivatives for the SI-SA-REKS method and implemented the method effectively on graphical processing units. We demonstrate that our implementation gives the correct conical intersection topography and energetics for several examples. Furthermore, our implementation of SI-SA-REKS is computationally efficient, with observed sub-quadratic scaling as a function of molecular size. This demonstrates the promise of SI-SA-REKS for excited state dynamics of large molecular systems.},
doi = {10.1063/5.0041389},
url = {https://www.osti.gov/biblio/1776568},
journal = {Journal of Chemical Physics},
issn = {ISSN 0021-9606},
number = {10},
volume = {154},
place = {United States},
publisher = {American Institute of Physics (AIP)},
year = {2021},
month = {03}}