Nonadiabatic Molecular Dynamics Study of the Relaxation Pathways of Photoexcited Cyclooctatetraene

Song, Huajing; Nam, Yeonsig; Keefer, Daniel; Garavelli, Marco; Mukamel, Shaul; Tretiak, Sergei

doi:10.1021/acs.jpclett.1c01397

Nonadiabatic Molecular Dynamics Study of the Relaxation Pathways of Photoexcited Cyclooctatetraene

Journal Article · Tue Jun 15 04:00:00 EDT 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.1c01397· OSTI ID:1922849

^[1]; Nam, Yeonsig ^[2]; Keefer, Daniel ^[2]; ^[3]; ^[2]; ^[4]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Regents, University of California, Irvine
Univ. of California, Irvine, CA (United States)
Univ. degli Studi di Bologna (Italy)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

In the current study, we present nonadiabatic (NAMD) and adiabatic molecular dynamics simulations of the transition-state dynamics of photoexcited cyclooctatetraene (COT). The equilibrium-state structure and absorption spectra are analyzed using the semiempirical Austin Model 1 potential. The NAMD simulations are obtained by a surface-hopping algorithm. We analyzed in detail an active excited to ground state relaxation pathway accompanied by an S₂/S₃(D_2d) → S₁(D_8h) → S_o(D_4h) → S_o(D_2d) double-bond shifting mechanism. The simulated excitation lifetime is in good agreement with experiment. The first excited singlet state S1 plays a crucial role in the photochemistry. Here, the obtained critical molecular conformations, energy barrier, and transition-state lifetime results will provide a basis for further investigations of the bond-order inversion and photoswitching process of COT.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Irvine, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0019484

OSTI ID:: 1922849

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 24 Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Intrinsically Competitive Photoinduced Polycyclization and Double-Bond Shift through a Boatlike Conical Intersection Garavelli, Marco; Bernardi, Fernando; Moliner, Vicente Angewandte Chemie International Edition, Vol. 40, Issue 8 https://doi.org/10.1002/1521-3773(20010417)40:8<1466::AID-ANIE1466>3.0.CO;2-R	journal	April 2001
Double-Bond Shifts in [4n]Annulenes as a New Principle for Molecular Switches: First Results with Dimethyl Heptalene-1,2- and -4,5-dicarboxylates Briquet, Anne Andr�e Sophie; Uebelhart, Peter; Hansen, Hans-J�rgen Helvetica Chimica Acta, Vol. 79, Issue 8 https://doi.org/10.1002/hlca.19960790819	journal	December 1996
Optimization of parameters for semiempirical methods IV: extension of MNDO, AM1, and PM3 to more main group elements Stewart, James J. P. Journal of Molecular Modeling, Vol. 10, Issue 2 https://doi.org/10.1007/s00894-004-0183-z	journal	April 2004
Implementation of surface hopping molecular dynamics using semiempirical methods Fabiano, E.; Keal, T. W.; Thiel, W. Chemical Physics, Vol. 349, Issue 1-3 https://doi.org/10.1016/j.chemphys.2008.01.044	journal	June 2008
Quantum transition state dynamics of the cyclooctatetraene unimolecular reaction on ab initio potential energy surfaces Tokizaki, Chihiro; Yoshida, Takahiko; Takayanagi, Toshiyuki Chemical Physics, Vol. 469-470 https://doi.org/10.1016/j.chemphys.2016.02.005	journal	May 2016
Theoretical analyses of the time-resolved nuclear dynamics of the transition state for the 1,3,5,7-cyclooctatetraene unimolecular reaction Tokizaki, Chihiro; Yoshida, Takahiko; Takayanagi, Toshiyuki Computational and Theoretical Chemistry, Vol. 1112 https://doi.org/10.1016/j.comptc.2017.04.010	journal	July 2017
Theoretical analysis of the transition-state spectrum of the cyclooctatetraene unimolecular reaction: Three degree-of-freedom model calculations Yoshida, Takahiko; Tokizaki, Chihiro; Takayanagi, Toshiyuki Chemical Physics Letters, Vol. 634 https://doi.org/10.1016/j.cplett.2015.06.018	journal	August 2015
A Historic Collaboration Savitzky, Abraham Analytical Chemistry, Vol. 61, Issue 15 https://doi.org/10.1021/ac00190a744	journal	August 1989
Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials Nelson, Tammie R.; White, Alexander J.; Bjorgaard, Josiah A. Chemical Reviews, Vol. 120, Issue 4 https://doi.org/10.1021/acs.chemrev.9b00447	journal	February 2020
NEXMD Software Package for Nonadiabatic Excited State Molecular Dynamics Simulations Malone, Walter; Nebgen, Benjamin; White, Alexander Journal of Chemical Theory and Computation, Vol. 16, Issue 9 https://doi.org/10.1021/acs.jctc.0c00248	journal	July 2020
First Principles Nonadiabatic Excited-State Molecular Dynamics in NWChem Song, Huajing; Fischer, Sean A.; Zhang, Yu Journal of Chemical Theory and Computation, Vol. 16, Issue 10 https://doi.org/10.1021/acs.jctc.0c00295	journal	August 2020
Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory Zhang, Yu; Mukamel, Shaul; Khalil, Munira Journal of Chemical Theory and Computation, Vol. 11, Issue 12 https://doi.org/10.1021/acs.jctc.5b00763	journal	November 2015
Quadratic Response Properties from TDDFT: Trials and Tribulations Parker, Shane M.; Rappoport, Dmitrij; Furche, Filipp Journal of Chemical Theory and Computation, Vol. 14, Issue 2 https://doi.org/10.1021/acs.jctc.7b01008	journal	December 2017
Theoretical Study of the Negative Ion Photoelectron Spectrum of Cyclooctatetraene via Computation of Franck–Condon Factors Chang, Jia-Lin; Cheng, Ming-Zhi; Huang, Yun-Jhu The Journal of Physical Chemistry A, Vol. 124, Issue 16 https://doi.org/10.1021/acs.jpca.0c01655	journal	April 2020
Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer Zheng, Fulu; Fernandez-Alberti, Sebastian; Tretiak, Sergei The Journal of Physical Chemistry B, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpcb.7b02021	journal	May 2017
The Future of Molecular Machines Aprahamian, Ivan ACS Central Science, Vol. 6, Issue 3 https://doi.org/10.1021/acscentsci.0c00064	journal	March 2020
The current view of dynamic change within cyclooctatetraenes Paquette, Leo A. Accounts of Chemical Research, Vol. 26, Issue 2 https://doi.org/10.1021/ar00026a004	journal	February 1993
Nonadiabatic Excited-State Molecular Dynamics: Modeling Photophysics in Organic Conjugated Materials Nelson, Tammie; Fernandez-Alberti, Sebastian; Roitberg, Adrian E. Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400263p	journal	February 2014
Nonadiabatic Ensemble Simulations of cis- Stilbene and cis -Azobenzene Photoisomerization Neukirch, Amanda J.; Shamberger, Logan C.; Abad, Enrique Journal of Chemical Theory and Computation, Vol. 10, Issue 1 https://doi.org/10.1021/ct4009816	journal	November 2013
Thermal and photochemical interconversions of cyclooctatetraenes and semibullvalenes. Exploratory organic photochemistry. LII Zimmerman, Howard E.; Iwamura, Hiizu. Journal of the American Chemical Society, Vol. 92, Issue 7 https://doi.org/10.1021/ja00710a038	journal	April 1970
Cyclooctatetraene Computational Photo- and Thermal Chemistry: A Reactivity Model for Conjugated Hydrocarbons Garavelli, Marco; Bernardi, Fernando; Cembran, Alessandro Journal of the American Chemical Society, Vol. 124, Issue 46 https://doi.org/10.1021/ja020741v	journal	November 2002
Isotope Effects on the Ring Inversion of Cyclooctatetraene Stevenson, Cheryl D.; Brown, Eric C.; Hrovat, David A. Journal of the American Chemical Society, Vol. 120, Issue 34 https://doi.org/10.1021/ja981496b	journal	September 1998
Nonadiabatic Excited-State Molecular Dynamics Modeling of Photoinduced Dynamics in Conjugated Molecules Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir The Journal of Physical Chemistry B, Vol. 115, Issue 18 https://doi.org/10.1021/jp109522g	journal	May 2011
Configuration Interaction-Corrected Tamm–Dancoff Approximation: A Time-Dependent Density Functional Method with the Correct Dimensionality of Conical Intersections Li, Shaohong L.; Marenich, Aleksandr V.; Xu, Xuefei The Journal of Physical Chemistry Letters, Vol. 5, Issue 2 https://doi.org/10.1021/jz402549p	journal	January 2014
Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation Parker, Shane M.; Roy, Saswata; Furche, Filipp Physical Chemistry Chemical Physics, Vol. 21, Issue 35 https://doi.org/10.1039/C9CP03127H	journal	January 2019
Ab initio non-adiabatic molecular dynamics Tapavicza, Enrico; Bellchambers, Gregory D.; Vincent, Jordan C. Physical Chemistry Chemical Physics, Vol. 15, Issue 42 https://doi.org/10.1039/c3cp51514a	journal	January 2013
The performance of semilocal and hybrid density functionals in 3d transition-metal chemistry Furche, Filipp; Perdew, John P. The Journal of Chemical Physics, Vol. 124, Issue 4 https://doi.org/10.1063/1.2162161	journal	January 2006
Electronic spectroscopy of 1,3,5,7‐cyclooctatetraene by low‐energy, variable‐angle electron impact Frueholz, Robert P.; Kuppermann, Aron The Journal of Chemical Physics, Vol. 69, Issue 8 https://doi.org/10.1063/1.437069	journal	October 1978
Molecular dynamics with electronic transitions Tully, John C. The Journal of Chemical Physics, Vol. 93, Issue 2 https://doi.org/10.1063/1.459170	journal	July 1990
Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules Fernandez-Alberti, Sebastian; Roitberg, Adrian E.; Nelson, Tammie The Journal of Chemical Physics, Vol. 137, Issue 1 https://doi.org/10.1063/1.4732536	journal	July 2012
Nonadiabatic excited-state molecular dynamics: Treatment of electronic decoherence Nelson, Tammie; Fernandez-Alberti, Sebastian; Roitberg, Adrian E. The Journal of Chemical Physics, Vol. 138, Issue 22 https://doi.org/10.1063/1.4809568	journal	June 2013
The electronically excited states of cyclooctatetraene—An analysis of the vacuum ultraviolet absorption spectrum by ab initio configuration interaction methods Palmer, Michael H.; Hoffmann, Søren Vrønning; Jones, Nykola C. The Journal of Chemical Physics, Vol. 151, Issue 8 https://doi.org/10.1063/1.5115997	journal	August 2019
Photoexcitation dynamics in perylene diimide dimers Mukazhanova, Aliya; Malone, Walter; Negrin-Yuvero, Hassiel The Journal of Chemical Physics, Vol. 153, Issue 24 https://doi.org/10.1063/5.0031485	journal	December 2020
Energetics and dynamics of a light-driven sodium-pumping rhodopsin Suomivuori, Carl-Mikael; Gamiz-Hernandez, Ana P.; Sundholm, Dage Proceedings of the National Academy of Sciences, Vol. 114, Issue 27 https://doi.org/10.1073/pnas.1703625114	journal	June 2017
Excitonic couplings and electronic coherence in bridged naphthalene dimers Tretiak, S.; Zhang, W. M.; Chernyak, V. Proceedings of the National Academy of Sciences, Vol. 96, Issue 23 https://doi.org/10.1073/pnas.96.23.13003	journal	November 1999
Conical intersections and double excitations in time-dependent density functional theory Levine, Benjamin G.; Ko, Chaehyuk; Quenneville, Jason Molecular Physics, Vol. 104, Issue 5-7 https://doi.org/10.1080/00268970500417762	journal	March 2006
Coherent electronic-vibrational dynamics in deuterium bromide probed via attosecond transient-absorption spectroscopy Kobayashi, Yuki; Chang, Kristina F.; Poullain, Sonia Marggi Physical Review A, Vol. 101, Issue 6 https://doi.org/10.1103/PhysRevA.101.063414	journal	June 2020
New Insights into the State Trapping of UV-Excited Thymine Stojanović, Ljiljana; Bai, Shuming; Nagesh, Jayashree Molecules, Vol. 21, Issue 11 https://doi.org/10.3390/molecules21111603	journal	November 2016
Recent Studies on the Aromaticity and Antiaromaticity of Planar Cyclooctatetraene Nishinaga, Tohru; Ohmae, Takeshi; Iyoda, Masahiko Symmetry, Vol. 2, Issue 1 https://doi.org/10.3390/sym2010076	journal	February 2010
Structures of Annulenes and Model Annulene Systems in the Ground and Lowest Excited States Gellini, Cristina; Salvi, Pier Remigio Symmetry, Vol. 2, Issue 4 https://doi.org/10.3390/sym2041846	journal	November 2010

Similar Records

Nonadiabatic Excited-State Molecular Dynamics for Open-Shell Systems

Journal Article · Sun Mar 01 23:00:00 EST 2020 · Journal of Chemical Theory and Computation · OSTI ID:1614840

Nonadiabatic Dynamics Simulation of the Wavelength-Dependent Photochemistry of Azobenzene Excited to the nπ* and ππ* Excited States

Journal Article · Sun Nov 22 23:00:00 EST 2020 · Journal of the American Chemical Society · OSTI ID:1779442

Excited-State and Nonadiabatic Molecular Dynamics Methods with Broad Applicability

Technical Report · Sun Feb 11 23:00:00 EST 2024 · OSTI ID:2283135

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical structure
Computational chemistry
Energy
Mathematical methods
Molecular dynamics

Nonadiabatic Molecular Dynamics Study of the Relaxation Pathways of Photoexcited Cyclooctatetraene

Citation Formats

References (40)

Similar Records

Related Subjects