Full-dimensional multi-state simulation of the photodissociation of thioanisole
Abstract
The photodissociation of thioanisole is very interesting because the experiments of Lim and Kim provide evidence for mode-specific effects on the product distribution. They showed that, with a specific S–CH3 stretching mode being excited as the reagent is excited to the S1 electronic state, there is a sharp increase in the proportion of the ground-state product to the excited-state product. In this work, we report 78 011 full-dimensional semiclassical multi-state trajectories of the photodissociation process using the coherent switching with decay of mixing dynamics method. The potential surfaces and couplings are based on electronic structure calculations that include dynamic correlation through second order perturbation theory. We report results for four sets of initial conditions, one corresponding roughly to 0–0 excitation and three corresponding to exciting one vibrational mode, to look for mode-specific effects. The simulations show no significant mode-specific effect on the product energy distributions, but they do show an effect on the distribution of minimum-energy gaps in the trajectories and on the lifetime for dissociation. In particular, excitation of the S–CH3 stretching mode leads to trajectories passing closer to the S1-S2 conical intersection and to shorter lifetimes. This provides a possible explanation of why experimental results are different formore »
- Authors:
-
[1];
[1]
- Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Inst.
- Publication Date:
- Research Org.:
- Univ. of New Mexico, Albuquerque, NM (United States); Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- Contributing Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- OSTI Identifier:
- 1474045
- Alternate Identifier(s):
- OSTI ID: 1373329
- Grant/Contract Number:
- SC0015997; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 147; Journal Issue: 4; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; band gap; photodissociation; chemical compounds and components; reaction rate constants; electronic structure methods; chemical elements; zero point energy; perturbation theory; vibrational spectra; potential energy surfaces
Citation Formats
Li, Shaohong L., and Truhlar, Donald G. Full-dimensional multi-state simulation of the photodissociation of thioanisole. United States: N. p., 2017.
Web. doi:10.1063/1.4994923.
Li, Shaohong L., & Truhlar, Donald G. Full-dimensional multi-state simulation of the photodissociation of thioanisole. United States. https://doi.org/10.1063/1.4994923
Li, Shaohong L., and Truhlar, Donald G. Fri .
"Full-dimensional multi-state simulation of the photodissociation of thioanisole". United States. https://doi.org/10.1063/1.4994923. https://www.osti.gov/servlets/purl/1474045.
@article{osti_1474045,
title = {Full-dimensional multi-state simulation of the photodissociation of thioanisole},
author = {Li, Shaohong L. and Truhlar, Donald G.},
abstractNote = {The photodissociation of thioanisole is very interesting because the experiments of Lim and Kim provide evidence for mode-specific effects on the product distribution. They showed that, with a specific S–CH3 stretching mode being excited as the reagent is excited to the S1 electronic state, there is a sharp increase in the proportion of the ground-state product to the excited-state product. In this work, we report 78 011 full-dimensional semiclassical multi-state trajectories of the photodissociation process using the coherent switching with decay of mixing dynamics method. The potential surfaces and couplings are based on electronic structure calculations that include dynamic correlation through second order perturbation theory. We report results for four sets of initial conditions, one corresponding roughly to 0–0 excitation and three corresponding to exciting one vibrational mode, to look for mode-specific effects. The simulations show no significant mode-specific effect on the product energy distributions, but they do show an effect on the distribution of minimum-energy gaps in the trajectories and on the lifetime for dissociation. In particular, excitation of the S–CH3 stretching mode leads to trajectories passing closer to the S1-S2 conical intersection and to shorter lifetimes. This provides a possible explanation of why experimental results are different for excitation of this vibration},
doi = {10.1063/1.4994923},
journal = {Journal of Chemical Physics},
number = 4,
volume = 147,
place = {United States},
year = {Fri Jul 28 00:00:00 EDT 2017},
month = {Fri Jul 28 00:00:00 EDT 2017}
}
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Works referenced in this record:
Coherent switching with decay of mixing: An improved treatment of electronic coherence for non-Born–Oppenheimer trajectories
journal, January 2004
- Zhu, Chaoyuan; Nangia, Shikha; Jasper, Ahren W.
- The Journal of Chemical Physics, Vol. 121, Issue 16
State selective photodissociation dynamics of A ̃ state ammonia. II
journal, September 1989
- Biesner, J.; Schnieder, L.; Ahlers, G.
- The Journal of Chemical Physics, Vol. 91, Issue 5
A Unified Perspective on the Hydrogen Atom Transfer and Proton-Coupled Electron Transfer Mechanisms in Terms of Topographic Features of the Ground and Excited Potential Energy Surfaces As Exemplified by the Reaction between Phenol and Radicals
journal, June 2008
- Tishchenko, Oksana; Truhlar, Donald G.; Ceulemans, Arnout
- Journal of the American Chemical Society, Vol. 130, Issue 22
Tuning photochemistry: substituent effects on πσ* state mediated bond fission in thioanisoles
journal, January 2015
- Wenge, Andreas M.; Karsili, Tolga N. V.; Rodríguez, Javier Diaz
- Physical Chemistry Chemical Physics, Vol. 17, Issue 25
Conical intersection seam and bound resonances embedded in continuum observed in the photodissociation of thioanisole-d 3
journal, February 2014
- Han, Songhee; Lim, Jeong Sik; Yoon, Jun-Ho
- The Journal of Chemical Physics, Vol. 140, Issue 5
Vibrationally mediated photodissociation of ammonia: The influence of N–H stretching vibrations on passage through conical intersections
journal, November 2006
- Hause, Michael L.; Yoon, Y. Heidi; Crim, F. Fleming
- The Journal of Chemical Physics, Vol. 125, Issue 17
Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole
journal, February 2017
- Li, Shaohong L.; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 146, Issue 6
Vibrationally mediated photodissociation of isocyanic acid (HNCO): Preferential N–H bond fission by excitation of the reaction coordinate
journal, October 1996
- Brown, Steven S.; Metz, Ricardo B.; Berghout, H. Laine
- The Journal of Chemical Physics, Vol. 105, Issue 15
An Improved Potential Energy Surface for the H 2 Cl System and Its Use for Calculations of Rate Coefficients and Kinetic Isotope Effects
journal, January 1996
- Allison, Thomas C.; Lynch, Gillian C.; Truhlar, Donald G.
- The Journal of Physical Chemistry, Vol. 100, Issue 32
Extension of the fourfold way for calculation of global diabatic potential energy surfaces of complex, multiarrangement, non-Born–Oppenheimer systems: Application to HNCO(S0,S1)
journal, April 2003
- Nakamura, Hisao; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 118, Issue 15
Model space diabatization for quantum photochemistry
journal, February 2015
- Li, Shaohong L.; Truhlar, Donald G.; Schmidt, Michael W.
- The Journal of Chemical Physics, Vol. 142, Issue 6
Control of Nonadiabatic Passage through a Conical Intersection by a Dynamic Resonance
journal, April 2016
- Epshtein, Michael; Yifrach, Yair; Portnov, Alexander
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
Decoherence in Combined Quantum Mechanical and Classical Mechanical Methods for Dynamics as Illustrated for Non-Born–Oppenheimer Trajectories
book, January 2007
- Truhlar, Donald G.
- Quantum Dynamics of Complex Molecular Systems
Dynamics at conical intersections: The influence of O–H stretching vibrations on the photodissociation of phenol
journal, March 2008
- Hause, Michael L.; Heidi Yoon, Y.; Case, Amanda S.
- The Journal of Chemical Physics, Vol. 128, Issue 10
State selective photodissociation dynamics of A ̃ state ammonia. I
journal, March 1988
- Biesner, J.; Schnieder, L.; Schmeer, J.
- The Journal of Chemical Physics, Vol. 88, Issue 6
Internal Conversion in Polyatomic Molecules
journal, January 1969
- Teller, E.
- Israel Journal of Chemistry, Vol. 7, Issue 2
Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling
journal, November 2014
- Xu, Xuefei; Zheng, Jingjing; Yang, Ke R.
- Journal of the American Chemical Society, Vol. 136, Issue 46
Rotationally resolved high-resolution spectrum of the S1–S0 transition of jet-cooled thioanisole
journal, January 2010
- Hoshino-Nagasaka, Mariko; Suzuki, Tadashi; Ichimura, Teijiro
- Physical Chemistry Chemical Physics, Vol. 12, Issue 40
Selectively breaking the O–H bond in HOD
journal, January 1990
- Vander Wal, R. L.; Scott, J. L.; Crim, F. F.
- The Journal of Chemical Physics, Vol. 92, Issue 1, p. 803-805
Exploring quantum phenomena and vibrational control in σ* mediated photochemistry
journal, January 2013
- Roberts, Gareth M.; Hadden, David J.; Bergendahl, L. Therese
- Chem. Sci., Vol. 4, Issue 3
Experimental probing of conical intersection dynamics in the photodissociation of thioanisole
journal, July 2010
- Lim, Jeong Sik; Kim, Sang Kyu
- Nature Chemistry, Vol. 2, Issue 8
Works referencing / citing this record:
Quantifying rival bond fission probabilities following photoexcitation: C–S bond fission in t -butylmethylsulfide
journal, January 2019
- Bain, Matthew; Hansen, Christopher S.; Karsili, Tolga N. V.
- Chemical Science, Vol. 10, Issue 20
Experimental observation of nonadiabatic bifurcation dynamics at resonances in the continuum
journal, January 2019
- Lim, Jean Sun; You, Hyun Sik; Kim, So-Yeon
- Chemical Science, Vol. 10, Issue 8
Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol
journal, October 2019
- Zhang, Linyao; Truhlar, Donald G.; Sun, Shaozeng
- The Journal of Chemical Physics, Vol. 151, Issue 15
Experimental observation of nonadiabatic bifurcation dynamics at resonances in the continuum
journal, January 2019
- Lim, Jean Sun; You, Hyun Sik; Kim, So-Yeon
- Chemical Science, Vol. 10, Issue 8
Non-adiabatic quantum reactive scattering in hyperspherical coordinates
journal, January 2018
- Kendrick, Brian K.
- The Journal of Chemical Physics, Vol. 148, Issue 4