Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time

Liu, Y.; Sanchez, D. M.; Ware, M. R.; Champenois, E. G.; Yang, J.; Nunes, J. P. F.; Attar, A.; Centurion, M.; Cryan, J. P.; Forbes, R.; Hegazy, K.; Hoffmann, M. C.; Ji, F.; Lin, M. -F.; Luo, D.; Saha, S. K.; Shen, X.; Wang, X. J.; Martínez, T. J.; Wolf, T. A.

doi:10.1038/s41467-023-38513-6

Title: Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time

Journal Article · 18 May 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-38513-6 · OSTI ID:1974288

^[1];

^[2]; Ware, M. R. ^[3]; Champenois, E. G. ^[3]; Yang, J. ^[4]; Nunes, J. P. F. ^[5]; Attar, A. ^[6];

^[7];

^[3];

^[8]; Hegazy, K. ^[3];

^[6]; Ji, F. ^[6];

^[6];

^[7];

^[6];

^[2];

^[3]

SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); Stony Brook University, NY (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); Stanford University, CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)
Tsinghua University, Beijing (China)
University of Nebraska, Lincoln, NE (United States); Harwell Science and Innovation Campus, Didcot (United Kingdom). Diamond Light Source
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
University of Nebraska, Lincoln, NE (United States)
Stanford University, CA (United States)

Electrocyclic reactions are characterized by the concerted formation and cleavage of both σ and π bonds through a cyclic structure. This structure is known as a pericyclic transition state for thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule α-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated π bonds. The σ bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.

View Journal Article

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231; AC52-07NA27344; SC0014170

OSTI ID:: 1974288

Alternate ID(s):: OSTI ID: 1971639; OSTI ID: 1984753

Report Number(s):: LLNL-JRNL-848870; TRN: US2313585

Journal Information:: Nature Communications, Vol. 14, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D ₃ Snyder, James W.; Curchod, Basile F. E.; Martínez, Todd J. The Journal of Physical Chemistry Letters, Vol. 7, Issue 13 https://doi.org/10.1021/acs.jpclett.6b00970	journal	June 2016
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction Minitti, M. P.; Budarz, J. M.; Kirrander, A. Physical Review Letters, Vol. 114, Issue 25 https://doi.org/10.1103/PhysRevLett.114.255501	journal	June 2015
Model calculations of photochemical reactivity Michl, J. Pure and Applied Chemistry, Vol. 41, Issue 4 https://doi.org/10.1351/pac197541040507	journal	January 1975
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
The Ultrafast Pathway of Photon-Induced Electrocyclic Ring-Opening Reactions: The Case of 1,3-Cyclohexadiene Deb, Sanghamitra; Weber, Peter M. Annual Review of Physical Chemistry, Vol. 62, Issue 1 https://doi.org/10.1146/annurev.physchem.012809.103350	journal	May 2011
Remarks on the specificities of the photochemical and thermal transformations in the vitamin D field Havinga, E.; Schlatmann, J. L. M. A. Tetrahedron, Vol. 16, Issue 1-4 https://doi.org/10.1016/0040-4020(61)80065-3	journal	January 1961
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 simulations for "Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time" Liu, Yusong; Sanchez, David M.; Ware, Matthew R. Zenodo https://doi.org/10.5281/zenodo.7854203	dataset	January 2023
The Conservation of Orbital Symmetry Woodward, R. B.; Hoffmann, Roald Angewandte Chemie International Edition in English, Vol. 8, Issue 11 https://doi.org/10.1002/anie.196907811	journal	November 1969
Ultrafast Imaging of Molecules with Electron Diffraction Centurion, Martin; Wolf, Thomas J. A.; Yang, Jie Annual Review of Physical Chemistry, Vol. 73, Issue 1 https://doi.org/10.1146/annurev-physchem-082720-010539	journal	April 2022
The influence of excited state topology on wavepacket delocalization in the relaxation of photoexcited polyatomic molecules Krause, Pascal; Matsika, Spiridoula; Kotur, Marija The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4748580	journal	December 2012
α-CASSCF: An Efficient, Empirical Correction for SA-CASSCF To Closely Approximate MS-CASPT2 Potential Energy Surfaces Snyder, James W.; Parrish, Robert M.; Martínez, Todd J. The Journal of Physical Chemistry Letters, Vol. 8, Issue 11 https://doi.org/10.1021/acs.jpclett.7b00940	journal	May 2017
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
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
The Transition State of the F + H2 Reaction Manolopoulos, D. E.; Stark, K.; Werner, H. -J. Science, Vol. 262, Issue 5141 https://doi.org/10.1126/science.262.5141.1852	journal	December 1993
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
Quantum-chemical interpretation of photo-induced electrocyclic reactions van der Lugt, W. Th. A. M.; Oosterhoff, L. J. Chemical Communications (London), Issue 20 https://doi.org/10.1039/C19680001235	journal	January 1968
On the ultrafast photo-induced dynamics of α-terpinene Gao, Yan; Pemberton, Christine C.; Zhang, Yao The Journal of Chemical Physics, Vol. 144, Issue 19 https://doi.org/10.1063/1.4948629	journal	May 2016
Feshbach resonances in the exit channel of the F + CH3OH → HF + CH3O reaction observed using transition-state spectroscopy Weichman, Marissa L.; DeVine, Jessalyn A.; Babin, Mark C. Nature Chemistry, Vol. 9, Issue 10 https://doi.org/10.1038/nchem.2804	journal	July 2017
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
Raw dataset for "Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time" Liu, Yusong; Sanchez, David M.; Ware, Matthew R. Zenodo https://doi.org/10.5281/zenodo.7570707	dataset	January 2023
Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory Weathersby, S. P.; Brown, G.; Centurion, M. Review of Scientific Instruments, Vol. 86, Issue 7 https://doi.org/10.1063/1.4926994	journal	July 2015
Ultrafast polyene dynamics: the ring opening of 1,3-cyclohexadiene derivatives Arruda, Brenden C.; Sension, Roseanne J. Physical Chemistry Chemical Physics, Vol. 16, Issue 10 https://doi.org/10.1039/c3cp54767a	journal	January 2014
Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction Attar, Andrew R.; Bhattacherjee, Aditi; Pemmaraju, C. D. Science, Vol. 356, Issue 6333 https://doi.org/10.1126/science.aaj2198	journal	April 2017
An atomic orbital-based formulation of analytical gradients and nonadiabatic coupling vector elements for the state-averaged complete active space self-consistent field method on graphical processing units Snyder, James W.; Hohenstein, Edward G.; Luehr, Nathan The Journal of Chemical Physics, Vol. 143, Issue 15 https://doi.org/10.1063/1.4932613	journal	October 2015
A direct-compatible formulation of the coupled perturbed complete active space self-consistent field equations on graphical processing units Snyder, James W.; Fales, B. Scott; Hohenstein, Edward G. The Journal of Chemical Physics, Vol. 146, Issue 17 https://doi.org/10.1063/1.4979844	journal	May 2017
Reaction Path of a sub-200 fs Photochemical Electrocyclic Reaction Garavelli, M.; Page, C. S.; Celani, P. The Journal of Physical Chemistry A, Vol. 105, Issue 18 https://doi.org/10.1021/jp010359p	journal	May 2001
Conformer-specific photochemistry imaged in real space and time Champenois, E. G.; Sanchez, D. M.; Yang, J. Science, Vol. 374, Issue 6564 https://doi.org/10.1126/science.abk3132	journal	October 2021
The Validity of the "Diradical" Hypothesis: Direct Femtoscond Studies of the Transition-State Structures Pedersen, S.; Herek, J. L.; Zewail, A. H. Science, Vol. 266, Issue 5189 https://doi.org/10.1126/science.266.5189.1359	journal	November 1994
Transition-State Spectroscopy of Cyclooctatetraene Wenthold, P. G.; Hrovat, D. A.; Borden, W. T. Science, Vol. 272, Issue 5267 https://doi.org/10.1126/science.272.5267.1456	journal	June 1996
Femtosecond gas-phase mega-electron-volt ultrafast electron diffraction Shen, X.; Nunes, J. P. F.; Yang, J. Structural Dynamics, Vol. 6, Issue 5 https://doi.org/10.1063/1.5120864	journal	September 2019
Quantum Chemistry on Graphical Processing Units. 2. Direct Self-Consistent-Field Implementation Ufimtsev, Ivan S.; Martinez, Todd J. Journal of Chemical Theory and Computation, Vol. 5, Issue 4 https://doi.org/10.1021/ct800526s	journal	March 2009
Symmetry control and photoinduced reactions Van der Lugt, W. Th. A. M.; Oosterhoff, Luitzen J. Journal of the American Chemical Society, Vol. 91, Issue 22 https://doi.org/10.1021/ja01050a019	journal	October 1969
Photochemical Ring-Opening and Ground State Relaxation in α-Terpinene with Comparison to Provitamin D₃ Arruda, Brenden C.; Peng, Jian; Smith, Broc The Journal of Physical Chemistry B, Vol. 117, Issue 16 https://doi.org/10.1021/jp308391u	journal	February 2013
Ultrafast ring-opening reactions: a comparison of α-terpinene, α-phellandrene, and 7-dehydrocholesterol with 1,3-cyclohexadiene Arruda, Brenden C.; Smith, Broc; Spears, Kenneth G. Faraday Discussions, Vol. 163 https://doi.org/10.1039/c3fd20149j	journal	January 2013
Raw dataset for "Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time" Liu, Yusong; Sanchez, David M.; Ware, Matthew R. Zenodo https://doi.org/10.5281/zenodo.7570707	dataset	January 2023
Ab initio multiple spawning simulations for "Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time" Liu, Yusong; Sanchez, David M.; Ware, Matthew R. Zenodo https://doi.org/10.5281/zenodo.7854203	dataset	January 2023

Similar Records

Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Journal Article · 2023 · Angewandte Chemie · OSTI ID:1975869

Leshchev, Denis; J. S. Valentine, Andrew; Kim, Pyosang; +14 more

Revealing Excited–State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Journal Article · 2023 · Angewandte Chemie (International Edition) · OSTI ID:1975882

Leshchev, Denis; Valentine, Andrew J. S.; Kim, Pyosang; +14 more

Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance

Journal Article · 2022 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1877452

Vermeeren, Pascal; Dalla Tiezza, Marco; Wolf, Mark E.; +5 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ultrafast electron diffraction
electrocyclic reactions
ab initio multiple spawning
photochemistry
chemical physics
reaction kinetics and dynamics
reaction mechanisms

Title: Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time

Citation Formats

References (38)

Similar Records

Related Subjects