The excited state dynamics of the s-trans-1,3-butadiene cation, focusing on the second and third bands of the photoelectron spectrum, have been investigated using a fully quantal approach, for the first time. The five lowest electronic states X2Bg, A2Au, B2Ag, C2Bu, and D2Ag considering the six vibrational modes S3, S5, S13, S17, S19, and S20 were taken into account in the nuclear quantum dynamical investigation. The potential energy curves have been calculated along these coordinates for the five lowest electronic states using the RS2C method. Our simulations indicate a moderately fast population transfer from the A2Au and B2Ag to the X2Bg state, taking place on a time scale of 70–80 fs. Furthermore, the computed second and third bands of the photoelectron spectrum are in good agreement with the corresponding experimental ones. Our calculation identifies the symmetric stretching of the central C—C bond S5 and the symmetric C—C—C bending S13 to be the main progression modes of the second and third bands of the photoelectron spectrum of (cationic) s-trans-1,3-butadiene.
Skip Nav Destination
Article navigation
14 September 2019
Research Article|
September 12 2019
Excited state dynamics of the s-trans-1, 3-butadiene cation: An ab initio quantum dynamical analysis
Behnam Nikoobakht
;
Behnam Nikoobakht
a)
1
School of Chemistry, The University of Sydney
, Sydney, Australia
Search for other works by this author on:
Andreas Dreuw
;
Andreas Dreuw
2
Interdisziplinäres Zentrum für Wissenschaftliches Rechnen, Universität Heidelberg
, Im Neuenheimer Feld 205, D-69120 Heidelberg, Germany
Search for other works by this author on:
Horst Köppel
Horst Köppel
3
Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg
, INF 229, D-69120 Heidelberg, Germany
Search for other works by this author on:
J. Chem. Phys. 151, 104105 (2019)
Article history
Received:
April 30 2019
Accepted:
August 16 2019
Citation
Behnam Nikoobakht, Andreas Dreuw, Horst Köppel; Excited state dynamics of the s-trans-1, 3-butadiene cation: An ab initio quantum dynamical analysis. J. Chem. Phys. 14 September 2019; 151 (10): 104105. https://doi.org/10.1063/1.5108610
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
453
Views
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
A quasiparticle-based multi-reference coupled-cluster method
J. Chem. Phys. (October 2014)
Assignment of photoelectron spectra of halide–water clusters: Contrasting patterns of delocalization in Dyson orbitals
J. Chem. Phys. (April 2013)
Investigation of the valence ionization spectrum of chromium carbonyl using an ab initio quantum dynamical approach
J. Chem. Phys. (February 2020)
Non-adiabatic quantum reactive scattering in hyperspherical coordinates
J. Chem. Phys. (January 2018)