Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
We combine recent advances in excited state variational principles, fast multi-Slater Jastrow methods and selective configuration interaction, to create multi-Slater Jastrow wave function approximations that are optimized for individual excited states. In addition to the Jastrow variables and linear expansion coefficients, this optimization includes state-specific orbital relaxations in order to avoid the compromises necessary in state-averaged approaches. Here, we demonstrate that, when combined with variance matching to help balance the quality of the approximation across different states, this approach delivers accurate excitation energies even when very modest multi-Slater expansions are used. Intriguingly, this accuracy is maintained even when we study a difficult chlorine-anion-to-π* charge transfer in which traditional state-averaged multireference methods must contend with different states that require drastically different orbital relaxations.
Pineda Flores, Sergio D. and Neuscamman, Eric. "Excited State Specific Multi-Slater Jastrow Wave Functions." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 123, no. 8, Jan. 2019. https://doi.org/10.1021/acs.jpca.8b10671
Pineda Flores, Sergio D., & Neuscamman, Eric (2019). Excited State Specific Multi-Slater Jastrow Wave Functions. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 123(8). https://doi.org/10.1021/acs.jpca.8b10671
Pineda Flores, Sergio D., and Neuscamman, Eric, "Excited State Specific Multi-Slater Jastrow Wave Functions," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 123, no. 8 (2019), https://doi.org/10.1021/acs.jpca.8b10671
@article{osti_1571973,
author = {Pineda Flores, Sergio D. and Neuscamman, Eric},
title = {Excited State Specific Multi-Slater Jastrow Wave Functions},
annote = {We combine recent advances in excited state variational principles, fast multi-Slater Jastrow methods and selective configuration interaction, to create multi-Slater Jastrow wave function approximations that are optimized for individual excited states. In addition to the Jastrow variables and linear expansion coefficients, this optimization includes state-specific orbital relaxations in order to avoid the compromises necessary in state-averaged approaches. Here, we demonstrate that, when combined with variance matching to help balance the quality of the approximation across different states, this approach delivers accurate excitation energies even when very modest multi-Slater expansions are used. Intriguingly, this accuracy is maintained even when we study a difficult chlorine-anion-to-π* charge transfer in which traditional state-averaged multireference methods must contend with different states that require drastically different orbital relaxations.},
doi = {10.1021/acs.jpca.8b10671},
url = {https://www.osti.gov/biblio/1571973},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {8},
volume = {123},
place = {United States},
publisher = {American Chemical Society},
year = {2019},
month = {01}}
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC02-05CH11231; NA0003864; AC02-06CH11357
OSTI ID:
1571973
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 8 Vol. 123; ISSN 1089-5639