eprintid: 10191903
rev_number: 7
eprint_status: archive
userid: 699
dir: disk0/10/19/19/03
datestamp: 2024-05-08 10:15:29
lastmod: 2024-05-08 10:15:29
status_changed: 2024-05-08 10:15:29
type: article
metadata_visibility: show
sword_depositor: 699
creators_name: Bennett, Olivia
creators_name: Freibert, Antonia
creators_name: Spinlove, K Eryn
creators_name: Worth, Graham A
title: Prediction through quantum dynamics simulations: Photo-excited cyclobutanone
ispublished: pub
divisions: UCL
divisions: B04
divisions: C06
divisions: F56
note: Copyright © 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/).
abstract: Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining experiments and giving details of non-adiabatic transitions, the question remains as to their predictive power. In this work, we present a set of quantum dynamics simulations on cyclobutanone using both grid-based multi-configuration time-dependent Hartree and direct dynamics variational multi-configuration Gaussian methods. The former used a parameterized vibronic coupling model Hamiltonian, and the latter generated the potential energy surfaces on the fly. The results give a picture of the non-adiabatic behavior of this molecule and were used to calculate the signal from a gas-phase ultrafast electron diffraction (GUED) experiment. Corresponding experimental results will be obtained and presented at a later stage for comparison to test the predictive power of the methods. The results show that over the first 500 fs after photo-excitation to the S2 state, cyclobutanone relaxes quickly to the S1 state, but only a small population relaxes further to the S0 state. No significant transfer of population to the triplet manifold is found. It is predicted that the GUED experiments over this time scale will see signals related mostly to the C–O stretch motion and elongation of the molecular ring along the C–C–O axis.
date: 2024-05-07
date_type: published
publisher: AIP Publishing
official_url: http://dx.doi.org/10.1063/5.0203654
oa_status: green
full_text_type: pub
language: eng
primo: open
primo_central: open_green
verified: verified_manual
elements_id: 2273300
doi: 10.1063/5.0203654
lyricists_name: Spinlove, Kaite
lyricists_name: Worth, Graham
lyricists_id: ESPIN94
lyricists_id: GWORT12
actors_name: Flynn, Bernadette
actors_id: BFFLY94
actors_role: owner
full_text_status: public
publication: The Journal of Chemical Physics
volume: 160
number: 17
article_number: 174305
issn: 0021-9606
citation:        Bennett, Olivia;    Freibert, Antonia;    Spinlove, K Eryn;    Worth, Graham A;      (2024)    Prediction through quantum dynamics simulations: Photo-excited cyclobutanone.                   The Journal of Chemical Physics , 160  (17)    , Article 174305.  10.1063/5.0203654 <https://doi.org/10.1063/5.0203654>.       Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/10191903/1/174305_1_5.0203654.pdf