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Title: Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations

The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 1 1B u (ππ*) state and non-adiabatically coupled dark 2 1A g state of BD. Importantly, AIMS allows for on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 1 1B u state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1B u or themore » dark 2 1A g state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [4] ; ORCiD logo [5] ;  [4] ; ORCiD logo [6]
  1. Stanford Univ., CA (United States). Dept. of Chemistry and the PULSE Inst.; SLAC National Accelerator Lab., Menlo Park, CA (United States); New York Univ., Shanghai (China). NYU-ECNU Center for Computational Chemistry; New York Univ. (NYU), NY (United States). Dept. of Chemistry
  2. Stanford Univ., CA (United States). Dept. of Chemistry and the PULSE Inst.; SLAC National Accelerator Lab., Menlo Park, CA (United States); Inst. for Molecular Science (IMS), Okazaki (Japan); Graduate Univ. for Advanced Studies (SOKENDAI), Hayama (Japan)
  3. National Research Council (NRC), Ottawa (Canada); Univ. of Ottawa (Canada). Dept. of Chemistry
  4. National Research Council (NRC), Ottawa (Canada); Univ. of Ottawa (Canada). Dept. of Chemistry and Dept. of Physics
  5. National Research Council (NRC), Ottawa (Canada); Stockholm Univ. (Sweden). Dept. of Physics and AlbaNova Univ. Center
  6. Stanford Univ., CA (United States). Dept. of Chemistry and the PULSE Inst.; SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Natural Sciences and Engineering Research Council of Canada (NSERC)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Spectroscopy; Photoionization; Molecular dynamics; Electronic structure calculations; Dark states; Potential energy surfaces; Radioactive decay; Chemical compounds
OSTI Identifier:
1438566
Alternate Identifier(s):
OSTI ID: 1434395

Glover, William J., Mori, Toshifumi, Schuurman, Michael S., Boguslavskiy, Andrey E., Schalk, Oliver, Stolow, Albert, and Martinez, Todd J.. Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations. United States: N. p., Web. doi:10.1063/1.5018130.
Glover, William J., Mori, Toshifumi, Schuurman, Michael S., Boguslavskiy, Andrey E., Schalk, Oliver, Stolow, Albert, & Martinez, Todd J.. Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations. United States. doi:10.1063/1.5018130.
Glover, William J., Mori, Toshifumi, Schuurman, Michael S., Boguslavskiy, Andrey E., Schalk, Oliver, Stolow, Albert, and Martinez, Todd J.. 2018. "Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations". United States. doi:10.1063/1.5018130.
@article{osti_1438566,
title = {Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations},
author = {Glover, William J. and Mori, Toshifumi and Schuurman, Michael S. and Boguslavskiy, Andrey E. and Schalk, Oliver and Stolow, Albert and Martinez, Todd J.},
abstractNote = {The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 11Bu (ππ*) state and non-adiabatically coupled dark 21Ag state of BD. Importantly, AIMS allows for on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 11Bu state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1Bu or the dark 21Ag state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.},
doi = {10.1063/1.5018130},
journal = {Journal of Chemical Physics},
number = 16,
volume = 148,
place = {United States},
year = {2018},
month = {4}
}