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

Yu, Jimmy K.; Bannwarth, Christoph; Liang, Ruibin; Hohenstein, Edward G.; Martínez, Todd J.

doi:10.1021/jacs.0c09056

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

Journal Article · Mon Nov 23 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c09056· OSTI ID:1779442

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Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Azobenzene is one of the most ubiquitous photoswitches in photochemistry and a prototypical model for photoisomerizing systems. Despite this, its wavelength-dependent photochemistry has puzzled researchers for decades. Upon excitation to the higher energy ππ* excited state instead of the dipole-forbidden nπ* state, the quantum yield of isomerization from trans- to cis-azobenzene is halved. The difficulties associated with unambiguously resolving this effect both experimentally and theoretically have contributed to lasting controversies regarding the photochemistry of azobenzene. Here, we systematically characterize the dynamic photoreaction pathways of azobenzene by performing first-principles simulations of the nonadiabatic dynamics following excitation to both the ππ* and the nπ* states. In this work, we demonstrate that ground-state recovery is mediated by two distinct S1 decay pathways: a reactive twisting pathway and an unreactive planar pathway. Increased preference for the unreactive pathway upon ππ* excitation largely accounts for the wavelength-dependent behavior observed in azobenzene.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: N00014-18-1-2624; AC02-76SF00515

OSTI ID:: 1779442

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 49; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Further evidence for rotation in the π,π* and inversion in the n,π* photoisomerization of azobenzenes Rau, Hermann Journal of Photochemistry, Vol. 26, Issue 2-3 https://doi.org/10.1016/0047-2670(84)80041-6	journal	August 1984
Quantum Chemistry on Graphical Processing Units. 2. Direct Self-Consistent-Field (SCF) Implementation Ufimtsev, Ivan S.; Martinez, Todd J. Journal of Chemical Theory and Computation, Vol. 5, Issue 11 https://doi.org/10.1021/ct900433g	journal	October 2009
Kasha's rule: a reappraisal del Valle, Juan Carlos; Catalán, Javier Physical Chemistry Chemical Physics, Vol. 21, Issue 19 https://doi.org/10.1039/C9CP00739C	journal	January 2019
Femtosecond Time-Resolved Fluorescence Study of Photoisomerization of trans -Azobenzene Fujino, Tatsuya; Arzhantsev, Sergei Yu.; Tahara, Tahei The Journal of Physical Chemistry A, Vol. 105, Issue 35 https://doi.org/10.1021/jp0110713	journal	September 2001
Light Switching of Molecules on Surfaces Browne, Wesley R.; Feringa, Ben L. Annual Review of Physical Chemistry, Vol. 60, Issue 1 https://doi.org/10.1146/annurev.physchem.040808.090423	journal	May 2009
Femtosecond/Picosecond Time-Resolved Spectroscopy of trans - Azobenzene: Isomerization Mechanism Following S ₂ (ππ*) ← S ₀ Photoexcitation Fujino, Tatsuya; Arzhantsev, Sergei Yu.; Tahara, Tahei Bulletin of the Chemical Society of Japan, Vol. 75, Issue 5 https://doi.org/10.1246/bcsj.75.1031	journal	May 2002
Hole–hole Tamm–Dancoff-approximated density functional theory: A highly efficient electronic structure method incorporating dynamic and static correlation Bannwarth, Christoph; Yu, Jimmy K.; Hohenstein, Edward G. The Journal of Chemical Physics, Vol. 153, Issue 2 https://doi.org/10.1063/5.0003985	journal	July 2020
Picosecond Time-Resolved Raman Study of trans -Azobenzene Fujino, Tatsuya; Tahara, Tahei The Journal of Physical Chemistry A, Vol. 104, Issue 18 https://doi.org/10.1021/jp992757m	journal	May 2000
UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans -Azobenzene Nenov, Artur; Borrego-Varillas, Rocio; Oriana, Aurelio The Journal of Physical Chemistry Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acs.jpclett.8b00152	journal	March 2018
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Quantum Chemistry on Graphical Processing Units. 1. Strategies for Two-Electron Integral Evaluation Ufimtsev, Ivan S.; Martínez, Todd J. Journal of Chemical Theory and Computation, Vol. 4, Issue 2 https://doi.org/10.1021/ct700268q	journal	January 2008
Simulation of the photodynamics of azobenzene on its first excited state: Comparison of full multiple spawning and surface hopping treatments Toniolo, A.; Ciminelli, C.; Persico, M. The Journal of Chemical Physics, Vol. 123, Issue 23 https://doi.org/10.1063/1.2134705	journal	December 2005
Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy Tan, Eric M. M.; Amirjalayer, Saeed; Smolarek, Szymon Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms6860	journal	January 2015
A perspective on the CASPT2 method Pulay, Peter International Journal of Quantum Chemistry, Vol. 111, Issue 13 https://doi.org/10.1002/qua.23052	journal	April 2011
Excited-State Decay in the Photoisomerisation of Azobenzene: A New Balance between Mechanisms Casellas, Josep; Bearpark, Michael J.; Reguero, Mar ChemPhysChem, Vol. 17, Issue 19 https://doi.org/10.1002/cphc.201600502	journal	August 2016
On the Quantum Correction For Thermodynamic Equilibrium Wigner, E. Physical Review, Vol. 40, Issue 5 https://doi.org/10.1103/PhysRev.40.749	journal	June 1932
Femtosecond time-resolved UV-visible absorption spectroscopy of trans-azobenzene: dependence on excitation wavelength Lednev, I. K.; Ye, T. -Q.; Matousek, P. Chemical Physics Letters, Vol. 290, Issue 1-3 https://doi.org/10.1016/S0009-2614(98)00490-4	journal	June 1998
TeraChem : A graphical processing unit ‐accelerated electronic structure package for large‐scale ab initio molecular dynamics Seritan, Stefan; Bannwarth, Christoph; Fales, Bryan S. WIREs Computational Molecular Science https://doi.org/10.1002/wcms.1494	journal	July 2020
Cis-trans photoisomerization of azobenzene. Solvent and triplet donors effects Bortolus, Pietro.; Monti, Sandra. The Journal of Physical Chemistry, Vol. 83, Issue 6 https://doi.org/10.1021/j100469a002	journal	March 1979
A new mixing of Hartree–Fock and local density‐functional theories Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464304	journal	January 1993
Clocking transient chemical changes by ultrafast electron diffraction Williamson, J. Charles; Cao, Jianming; Ihee, Hyotcherl Nature, Vol. 386, Issue 6621 https://doi.org/10.1038/386159a0	journal	March 1997
Multiconfiguration second-order perturbation theory approach to strong electron correlation in chemistry and photochemistry: Multiconfiguration second-order perturbation theory Roca-Sanjuán, Daniel; Aquilante, Francesco; Lindh, Roland Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4 https://doi.org/10.1002/wcms.97	journal	November 2011
Theoretical study on the photoisomerization of azobenzene Ishikawa, Takeshi; Noro, Takeshi; Shoda, Takayuki The Journal of Chemical Physics, Vol. 115, Issue 16 https://doi.org/10.1063/1.1406975	journal	October 2001
Molecular Switches and Motors on Surfaces Pathem, Bala Krishna; Claridge, Shelley A.; Zheng, Yue Bing Annual Review of Physical Chemistry, Vol. 64, Issue 1 https://doi.org/10.1146/annurev-physchem-040412-110045	journal	April 2013
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
On the rotation-inversion controversy on photoisomerization of azobenzenes. Experimental proof of inversion Rau, Hermann; Lueddecke, Erik Journal of the American Chemical Society, Vol. 104, Issue 6 https://doi.org/10.1021/ja00370a028	journal	March 1982
Photoisomerization Dynamics and Pathways of trans - and cis -Azobenzene in Solution from Broadband Femtosecond Spectroscopies and Calculations Quick, M.; Dobryakov, A. L.; Gerecke, M. The Journal of Physical Chemistry B, Vol. 118, Issue 29 https://doi.org/10.1021/jp504999f	journal	July 2014
Reversible Photocontrol of Biological Systems by the Incorporation of Molecular Photoswitches Szymański, Wiktor; Beierle, John M.; Kistemaker, Hans A. V. Chemical Reviews, Vol. 113, Issue 8, p. 6114-6178 https://doi.org/10.1021/cr300179f	journal	April 2013
On the Mechanism of the cis−trans Isomerization in the Lowest Electronic States of Azobenzene: S ₀ , S ₁ , and T ₁ Cembran, Alessandro; Bernardi, Fernando; Garavelli, Marco Journal of the American Chemical Society, Vol. 126, Issue 10 https://doi.org/10.1021/ja038327y	journal	March 2004
Why Does trans -Azobenzene Have a Smaller Isomerization Yield for ππ* Excitation Than for nπ* Excitation? Yuan, Shuai; Dou, Yusheng; Wu, Weifeng The Journal of Physical Chemistry A, Vol. 112, Issue 51 https://doi.org/10.1021/jp806227x	journal	December 2008
Ultrafast dynamics and photochemistry of π-π* excited trans -azobenzene-a comprehensive analysis of resonance Raman intensities Chowdary, P. D.; Umapathy, S. Journal of Raman Spectroscopy, Vol. 39, Issue 11 https://doi.org/10.1002/jrs.2072	journal	November 2008
The Different Photoisomerization Efficiency of Azobenzene in the Lowest nπ* and ππ* Singlets: The Role of a Phantom State Conti, Irene; Garavelli, Marco; Orlandi, Giorgio Journal of the American Chemical Society, Vol. 130, Issue 15 https://doi.org/10.1021/ja710275e	journal	April 2008
Features of the photochemically active state surfaces of azobenzene Monti, Sandra; Orlandi, Giorgio; Palmieri, Paolo Chemical Physics, Vol. 71, Issue 1 https://doi.org/10.1016/0301-0104(82)87008-0	journal	September 1982
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Imaging CF ₃ I conical intersection and photodissociation dynamics with ultrafast electron diffraction Yang, Jie; Zhu, Xiaolei; Wolf, Thomas J. A. Science, Vol. 361, Issue 6397 https://doi.org/10.1126/science.aat0049	journal	July 2018
Mapping Atomic Motions with Ultrabright Electrons: The Chemists' Gedanken Experiment Enters the Lab Frame Miller, R. J. Dwayne Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040412-110117	journal	April 2014
Probing the π → π* photoisomerization mechanism of trans -azobenzene by multi-state ab initio on-the-fly trajectory dynamics simulations Xu, Chao; Yu, Le; Gu, Feng Long Physical Chemistry Chemical Physics, Vol. 20, Issue 37 https://doi.org/10.1039/C8CP02767F	journal	January 2018
Characterization of electronic transitions in complex molecules Kasha, Michael Discussions of the Faraday Society, Vol. 9 https://doi.org/10.1039/df9500900014	journal	January 1950
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Simultaneous observation of nuclear and electronic dynamics by ultrafast electron diffraction Yang, Jie; Zhu, Xiaolei; F. Nunes, J. Pedro Science, Vol. 368, Issue 6493 https://doi.org/10.1126/science.abb2235	journal	May 2020
The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction Wolf, T. J. A.; Sanchez, D. M.; Yang, J. Nature Chemistry, Vol. 11, Issue 6 https://doi.org/10.1038/s41557-019-0252-7	journal	April 2019
Ab Initio Multiple Spawning: Photochemistry from First Principles Quantum Molecular Dynamics Ben-Nun, M.; Quenneville, Jason; Martínez, Todd J. The Journal of Physical Chemistry A, Vol. 104, Issue 22 https://doi.org/10.1021/jp994174i	journal	June 2000
Cooperating Dinitrogen and Phenyl Rotations in trans- Azobenzene Photoisomerization Gámez, José A.; Weingart, Oliver; Koslowski, Axel Journal of Chemical Theory and Computation, Vol. 8, Issue 7 https://doi.org/10.1021/ct300303s	journal	June 2012
cis .dblharw. trans Photoisomerization of azobenzene-cyclodextrin inclusion complexes Bortolus, Pietro.; Monti, Sandra. The Journal of Physical Chemistry, Vol. 91, Issue 19 https://doi.org/10.1021/j100303a032	journal	September 1987
Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics Ufimtsev, Ivan S.; Martinez, Todd J. Journal of Chemical Theory and Computation, Vol. 5, Issue 10 https://doi.org/10.1021/ct9003004	journal	August 2009
Ab initio molecular dynamics simulation of photoisomerization in azobenzene in the nπ[sup ∗] state Ootani, Yusuke; Satoh, Kiminori; Nakayama, Akira The Journal of Chemical Physics, Vol. 131, Issue 19 https://doi.org/10.1063/1.3263918	journal	January 2009
The Photoisomerization Mechanism of Azobenzene: A Semiclassical Simulation of Nonadiabatic Dynamics Ciminelli, Cosimo; Granucci, Giovanni; Persico, Maurizio Chemistry - A European Journal, Vol. 10, Issue 9 https://doi.org/10.1002/chem.200305415	journal	May 2004
Nonadiabatic molecular dynamics: Validation of the multiple spawning method for a multidimensional problem Ben-Nun, M.; Martı́nez, Todd J. The Journal of Chemical Physics, Vol. 108, Issue 17 https://doi.org/10.1063/1.476142	journal	May 1998
Ab Initio Quantum Molecular Dynamics Ben-Nun, Michal; Martínez, Todd. J. Advances in Chemical Physics, Volume 121 https://doi.org/10.1002/0471264318.ch7	book	January 2002
Mechanism and Dynamics of Azobenzene Photoisomerization Schultz, Thomas; Quenneville, Jason; Levine, Benjamin Journal of the American Chemical Society, Vol. 125, Issue 27 https://doi.org/10.1021/ja021363x	journal	July 2003
Multidimensional Potential Energy Surfaces Resolved at the RASPT2 Level for Accurate Photoinduced Isomerization Dynamics of Azobenzene Aleotti, Flavia; Soprani, Lorenzo; Nenov, Artur Journal of Chemical Theory and Computation, Vol. 15, Issue 12 https://doi.org/10.1021/acs.jctc.9b00561	journal	October 2019
Femtosecond Time-Resolved UV−Visible Absorption Spectroscopy of trans -Azobenzene in Solution Lednev, Igor K.; Ye, Tian-Qing; Hester, Ronald E. The Journal of Physical Chemistry, Vol. 100, Issue 32 https://doi.org/10.1021/jp9610067	journal	January 1996
How Does the Trans-Cis Photoisomerization of Azobenzene Take Place in Organic Solvents? Tiberio, Giustiniano; Muccioli, Luca; Berardi, Roberto ChemPhysChem, Vol. 11, Issue 5 https://doi.org/10.1002/cphc.200900652	journal	March 2010
Excited-State Structure and Dynamics of cis - and trans -Azobenzene from Resonance Raman Intensity Analysis Stuart, Christina M.; Frontiera, Renee R.; Mathies, Richard A. The Journal of Physical Chemistry A, Vol. 111, Issue 48 https://doi.org/10.1021/jp0751460	journal	December 2007
Ab Initio Nonadiabatic Molecular Dynamics with Hole–Hole Tamm–Dancoff Approximated Density Functional Theory Yu, Jimmy K.; Bannwarth, Christoph; Hohenstein, Edward G. Journal of Chemical Theory and Computation, Vol. 16, Issue 9 https://doi.org/10.1021/acs.jctc.0c00644	journal	August 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Energy
Azobenzene
Quantum mechanics
Mathematical methods
Photochemistry

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

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