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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5018130· OSTI ID:1438566
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)
+ Show Author Affiliations

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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Natural Sciences and Engineering Research Council of Canada (NSERC)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1438566
Alternate ID(s):
OSTI ID: 1434395
Journal Information:
Journal of Chemical Physics, Vol. 148, Issue 16; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

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Cited By (9)

Different flavors of nonadiabatic molecular dynamics journal April 2019
Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy journal April 2018
The ring-opening channel and the influence of Rydberg states on the excited state dynamics of furan and its derivatives journal August 2018
The simulation of X-ray absorption spectra from ground and excited electronic states using core-valence separated DFT/MRCI journal October 2019
Analytical gradients and derivative couplings for dynamically weighted complete active space self-consistent field journal November 2019
Excited-state dynamics of molecules with classically driven trajectories and Gaussians journal September 2019
A strong enhancement in electronic current due to conical-intersection journal September 2019
Excited-state dynamics of molecules with classically driven trajectories and Gaussians text January 2019
Excited-state dynamics of molecules with classically driven trajectories and Gaussians text January 2019

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Related Subjects

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