Exploring the impact of vibrational cavity coupling strength on ultrafast CN + c -C 6 H 12 reaction dynamics

Chen, Liying; Fidler, Ashley P.; McKillop, Alexander M.; Weichman, Marissa L.

doi:10.1515/nanoph-2023-0747

Title: Exploring the impact of vibrational cavity coupling strength on ultrafast CN + c -C ₆ H ₁₂ reaction dynamics

Journal Article · 24 January 2024 · Nanophotonics (Online)

DOI: https://doi.org/10.1515/nanoph-2023-0747 · OSTI ID:2282825

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Department of Chemistry , Princeton University , Princeton , NJ , USA

Abstract Molecular polaritons, hybrid light-matter states resulting from strong cavity coupling of optical transitions, may provide a new route to guide chemical reactions. However, demonstrations of cavity-modified reactivity in clean benchmark systems are still needed to clarify the mechanisms and scope of polariton chemistry. Here, we use transient absorption to observe the ultrafast dynamics of CN radicals interacting with a cyclohexane ( c -C ₆ H ₁₂ ) and chloroform (CHCl ₃ ) solvent mixture under vibrational strong coupling of a C–H stretching mode of c- C ₆ H ₁₂ . By modulating the c -C ₆ H ₁₂ :CHCl ₃ ratio, we explore how solvent complexation and hydrogen (H)-abstraction processes proceed under collective cavity coupling strengths ranging from 55 to 85 cm ⁻¹ . Reaction rates remain unchanged for all extracavity, on-resonance, and off-resonance cavity coupling conditions, regardless of coupling strength. These results suggest that insufficient vibrational cavity coupling strength may not be the determining factor for the negligible cavity effects observed previously in H-abstraction reactions of CN with CHCl ₃ .

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Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022948

OSTI ID:: 2282825

Journal Information:: Nanophotonics (Online), Journal Name: Nanophotonics (Online) Journal Issue: 14 Vol. 13; ISSN 2192-8614

Publisher:: Walter de Gruyter GmbHCopyright Statement

Country of Publication:: Germany

Language:: English

References (58)

Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field Thomas, Anoop; George, Jino; Shalabney, Atef Angewandte Chemie International Edition, Vol. 55, Issue 38 https://doi.org/10.1002/anie.201605504	journal	August 2016
Modulation of Prins Cyclization by Vibrational Strong Coupling Hirai, Kenji; Takeda, Rie; Hutchison, James A. Angewandte Chemie International Edition, Vol. 59, Issue 13 https://doi.org/10.1002/anie.201915632	journal	February 2020
Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling Sau, Abhijit; Nagarajan, Kalaivanan; Patrahau, Bianca Angewandte Chemie International Edition, Vol. 60, Issue 11 https://doi.org/10.1002/anie.202013465	journal	February 2021
Quantum Control of Gas-Phase and Liquid-Phase Femtochemistry Brixner, Tobias; Gerber, Gustav ChemPhysChem, Vol. 4, Issue 5 https://doi.org/10.1002/cphc.200200581	journal	May 2003
Femtochemistry of ICN in liquids: dynamics of dissociation, recombination and abstraction Wan, Choazhi; Gupta, Manish; Zewail, Ahmed H. Chemical Physics Letters, Vol. 256, Issue 3 https://doi.org/10.1016/0009-2614(96)00443-5	journal	June 1996
On the use of two-photon absorption for determination of femtosecond pump–probe cross-correlation functions Rasmusson, Marcus; Tarnovsky, Alexander N.; Åkesson, Eva Chemical Physics Letters, Vol. 335, Issue 3-4 https://doi.org/10.1016/S0009-2614(01)00057-4	journal	February 2001
Molecular Vibrational Polariton Dynamics: What Can Polaritons Do? Xiong, Wei Accounts of Chemical Research, Vol. 56, Issue 7 https://doi.org/10.1021/acs.accounts.2c00796	journal	March 2023
Control, Modulation, and Analytical Descriptions of Vibrational Strong Coupling Simpkins, Blake S.; Dunkelberger, Adam D.; Vurgaftman, Igor Chemical Reviews, Vol. 123, Issue 8 https://doi.org/10.1021/acs.chemrev.2c00774	journal	April 2023
Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics Mandal, Arkajit; Taylor, Michael A. D.; Weight, Braden M. Chemical Reviews, Vol. 123, Issue 16 https://doi.org/10.1021/acs.chemrev.2c00855	journal	August 2023
Cyclohexane Vibrations: High-Resolution Spectra and Anharmonic Local Mode Calculations Bernath, Peter F.; Sibert III, Edwin L. The Journal of Physical Chemistry A, Vol. 124, Issue 48 https://doi.org/10.1021/acs.jpca.0c09185	journal	November 2020
Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents Coulter, Philip; Grubb, Michael P.; Koyama, Daisuke The Journal of Physical Chemistry A, Vol. 119, Issue 52 https://doi.org/10.1021/acs.jpca.5b10716	journal	December 2015
First Evidence of Vibrationally Driven Bimolecular Reactions in Solution: Reactions of Br Atoms with Dimethylsulfoxide and Methanol Shin, Jae Yoon; Shaloski, Michael A.; Crim, F. Fleming The Journal of Physical Chemistry B, Vol. 121, Issue 11 https://doi.org/10.1021/acs.jpcb.7b00035	journal	March 2017
Mode-Specific Chemistry through Vibrational Strong Coupling (or A Wish Come True) Simpkins, Blake S.; Dunkelberger, Adam D.; Owrutsky, Jeffrey C. The Journal of Physical Chemistry C, Vol. 125, Issue 35 https://doi.org/10.1021/acs.jpcc.1c05362	journal	August 2021
Cavity-Modified Unimolecular Dissociation Reactions via Intramolecular Vibrational Energy Redistribution Wang, Derek S.; Neuman, Tomáš; Yelin, Susanne F. The Journal of Physical Chemistry Letters, Vol. 13, Issue 15 https://doi.org/10.1021/acs.jpclett.2c00558	journal	April 2022
Suppression and Enhancement of Thermal Chemical Rates in a Cavity Sun, Jing; Vendrell, Oriol The Journal of Physical Chemistry Letters, Vol. 13, Issue 20 https://doi.org/10.1021/acs.jpclett.2c00974	journal	May 2022
Theory for Nonlinear Spectroscopy of Vibrational Polaritons F. Ribeiro, Raphael; Dunkelberger, Adam D.; Xiang, Bo The Journal of Physical Chemistry Letters, Vol. 9, Issue 13 https://doi.org/10.1021/acs.jpclett.8b01176	journal	May 2018
A Roadmap Toward the Theory of Vibrational Polariton Chemistry Wang, Derek S.; Yelin, Susanne F. ACS Photonics, Vol. 8, Issue 10 https://doi.org/10.1021/acsphotonics.1c01028	journal	September 2021
Spanning Strong to Weak Normal Mode Coupling between Vibrational and Fabry–Pérot Cavity Modes through Tuning of Vibrational Absorption Strength Simpkins, B. S.; Fears, Kenan P.; Dressick, Walter J. ACS Photonics, Vol. 2, Issue 10 https://doi.org/10.1021/acsphotonics.5b00324	journal	September 2015
Controlling the Future of Matter Kohler, Bern; Krause, Jeffrey L.; Raksi, Ferenc Accounts of Chemical Research, Vol. 28, Issue 3 https://doi.org/10.1021/ar00051a006	journal	March 1995
Vibrational State Control of Bimolecular Reactions: Discovering and Directing the Chemistry Crim, F. Fleming Accounts of Chemical Research, Vol. 32, Issue 10 https://doi.org/10.1021/ar950046a	journal	October 1999
The Influence of Vibrational Excitation on the Photoisomerization of trans-Stilbene in Solution Briney, Kristin A.; Herman, Leslie; Boucher, David S. The Journal of Physical Chemistry A, Vol. 114, Issue 36 https://doi.org/10.1021/jp102752f	journal	July 2010
Time-Resolved Studies of CN Radical Reactions and the Role of Complexes in Solution Crowther, Andrew C.; Carrier, Stacey L.; Preston, Thomas J. The Journal of Physical Chemistry A, Vol. 112, Issue 47 https://doi.org/10.1021/jp8064079	journal	November 2008
Time-Resolved Studies of the Reactions of CN Radical Complexes with Alkanes, Alcohols, and Chloroalkanes Crowther, Andrew C.; Carrier, Stacey L.; Preston, Thomas J. The Journal of Physical Chemistry A, Vol. 113, Issue 16 https://doi.org/10.1021/jp8084099	journal	January 2009
Bond-Selected Chemistry: Vibrational State Control of Photodissociation and Bimolecular Reaction Crim, F. Fleming The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp9604812	journal	January 1996
Ultrafast energy flow in the wake of solution-phase bimolecular reactions Glowacki, David R.; Rose, Rebecca A.; Greaves, Stuart J. Nature Chemistry, Vol. 3, Issue 11 https://doi.org/10.1038/nchem.1154	journal	September 2011
Acceleration of a ground-state reaction by selective femtosecond-infrared-laser-pulse excitation Stensitzki, Till; Yang, Yang; Kozich, Valeri Nature Chemistry, Vol. 10, Issue 2 https://doi.org/10.1038/nchem.2909	journal	January 2018
Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity Schäfer, Christian; Flick, Johannes; Ronca, Enrico Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-35363-6	journal	December 2022
Taking the plunge: chemical reaction dynamics in liquids Orr-Ewing, Andrew J. Chemical Society Reviews, Vol. 46, Issue 24 https://doi.org/10.1039/C7CS00331E	journal	January 2017
Strong light–matter interactions: a new direction within chemistry Hertzog, Manuel; Wang, Mao; Mony, Jürgen Chemical Society Reviews, Vol. 48, Issue 3 https://doi.org/10.1039/C8CS00193F	journal	January 2019
Polariton chemistry: controlling molecular dynamics with optical cavities Ribeiro, Raphael F.; Martínez-Martínez, Luis A.; Du, Matthew Chemical Science, Vol. 9, Issue 30 https://doi.org/10.1039/C8SC01043A	journal	January 2018
The photoisomerization of aqueous ICN studied by subpicosecond transient absorption spectroscopy Larsen, Jane; Madsen, Dorte; Poulsen, Jens-Aage The Journal of Chemical Physics, Vol. 116, Issue 18 https://doi.org/10.1063/1.1467897	journal	April 2002
Photodissociation of ICN in polar solvents: Evidence for long lived rotational excitation in room temperature liquids Moskun, Amy C.; Bradforth, Stephen E. The Journal of Chemical Physics, Vol. 119, Issue 8 https://doi.org/10.1063/1.1591726	journal	August 2003
Product energy deposition of CN + alkane H abstraction reactions in gas and solution phases Glowacki, David R.; Orr-Ewing, Andrew J.; Harvey, Jeremy N. The Journal of Chemical Physics, Vol. 134, Issue 21 https://doi.org/10.1063/1.3595259	journal	June 2011
Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution Rose, Rebecca A.; Greaves, Stuart J.; Oliver, Thomas A. A. The Journal of Chemical Physics, Vol. 134, Issue 24 https://doi.org/10.1063/1.3603966	journal	June 2011
Molecular polaritons for controlling chemistry with quantum optics Herrera, Felipe; Owrutsky, Jeffrey The Journal of Chemical Physics, Vol. 152, Issue 10 https://doi.org/10.1063/1.5136320	journal	March 2020
Reproducibility of cavity-enhanced chemical reaction rates in the vibrational strong coupling regime Imperatore, Mario V.; Asbury, John B.; Giebink, Noel C. The Journal of Chemical Physics, Vol. 154, Issue 19 https://doi.org/10.1063/5.0046307	journal	May 2021
Cavity-altered thermal isomerization rates and dynamical resonant localization in vibro-polaritonic chemistry Fischer, Eric W.; Anders, Janet; Saalfrank, Peter The Journal of Chemical Physics, Vol. 156, Issue 15 https://doi.org/10.1063/5.0076434	journal	April 2022
Negligible rate enhancement from reported cooperative vibrational strong coupling catalysis Wiesehan, Garret D.; Xiong, Wei The Journal of Chemical Physics, Vol. 155, Issue 24 https://doi.org/10.1063/5.0077549	journal	December 2021
Dissociation dynamics of a diatomic molecule in an optical cavity Mondal, Subhadip; Wang, Derek S.; Keshavamurthy, Srihari The Journal of Chemical Physics, Vol. 157, Issue 24 https://doi.org/10.1063/5.0124085	journal	December 2022
Swinging between shine and shadow: Theoretical advances on thermally activated vibropolaritonic chemistry Campos-Gonzalez-Angulo, J. A.; Poh, Y. R.; Du, M. The Journal of Chemical Physics, Vol. 158, Issue 23 https://doi.org/10.1063/5.0143253	journal	June 2023
Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling Fidler, Ashley P.; Chen, Liying; McKillop, Alexander M. The Journal of Chemical Physics, Vol. 159, Issue 16 https://doi.org/10.1063/5.0167410	journal	October 2023
Strong coupling between surface plasmon polaritons and emitters: a review Törmä, P.; Barnes, W. L. Reports on Progress in Physics, Vol. 78, Issue 1 https://doi.org/10.1088/0034-4885/78/1/013901	journal	December 2014
Quantum Electronics for Atomic Physics and Telecommunication (2nd edition) Nagourney, Warren https://doi.org/10.1093/acprof:oso/9780199665488.001.0001	journal	May 2014
Vacuum Rabi splitting as a feature of linear-dispersion theory: Analysis and experimental observations Zhu, Yifu; Gauthier, Daniel J.; Morin, S. E. Physical Review Letters, Vol. 64, Issue 21 https://doi.org/10.1103/PhysRevLett.64.2499	journal	May 1990
Nonlinear optics of normal-mode-coupling semiconductor microcavities Khitrova, G.; Gibbs, H. M.; Jahnke, F. Reviews of Modern Physics, Vol. 71, Issue 5 https://doi.org/10.1103/RevModPhys.71.1591	journal	October 1999
Exciton-polariton Bose-Einstein condensation Deng, Hui; Haug, Hartmut; Yamamoto, Yoshihisa Reviews of Modern Physics, Vol. 82, Issue 2 https://doi.org/10.1103/RevModPhys.82.1489	journal	May 2010
Accurate optical constants for liquids in the near-infrared:Improved methods for obtaining the n and k constants from 1 to 4 µm Myers, Tanya L.; Tonkyn, Russell G.; Loring, John S. Chemical, Biological, Radiological, Nuclear, and Explosives (CBRNE) Sensing XX https://doi.org/10.1117/12.2519499	conference	May 2019
Bond-Selective Control of a Heterogeneously Catalyzed Reaction Killelea, D. R.; Campbell, V. L.; Shuman, N. S. Science, Vol. 319, Issue 5864 https://doi.org/10.1126/science.1152819	journal	February 2008
Vibrationally Quantum-State–Specific Reaction Dynamics of H Atom Abstraction by CN Radical in Solution Greaves, Stuart J.; Rose, Rebecca A.; Oliver, Thomas A. A. Science, Vol. 331, Issue 6023 https://doi.org/10.1126/science.1197796	journal	March 2011
Laser Control of Chemical Reactions Zare, Richard N. Science, Vol. 279, Issue 5358, p. 1875-1879 https://doi.org/10.1126/science.279.5358.1875	journal	March 1998
Tilting a ground-state reactivity landscape by vibrational strong coupling Thomas, A.; Lethuillier-Karl, L.; Nagarajan, K. Science, Vol. 363, Issue 6427 https://doi.org/10.1126/science.aau7742	journal	February 2019
Manipulating matter by strong coupling to vacuum fields Garcia-Vidal, Francisco J.; Ciuti, Cristiano; Ebbesen, Thomas W. Science, Vol. 373, Issue 6551 https://doi.org/10.1126/science.abd0336	journal	July 2021
Cavity-enabled enhancement of ultrafast intramolecular vibrational redistribution over pseudorotation Chen, Teng-Teng; Du, Matthew; Yang, Zimo Science, Vol. 378, Issue 6621 https://doi.org/10.1126/science.add0276	journal	November 2022
Modification of ground-state chemical reactivity via light–matter coherence in infrared cavities Ahn, Wonmi; Triana, Johan F.; Recabal, Felipe Science, Vol. 380, Issue 6650 https://doi.org/10.1126/science.ade7147	journal	June 2023
Dynamics of Bimolecular Reactions in Solution Orr-Ewing, Andrew J. Annual Review of Physical Chemistry, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-physchem-040214-121654	journal	April 2015
Vibration-Cavity Polariton Chemistry and Dynamics Dunkelberger, Adam D.; Simpkins, Blake S.; Vurgaftman, Igor Annual Review of Physical Chemistry, Vol. 73, Issue 1 https://doi.org/10.1146/annurev-physchem-082620-014627	journal	April 2022
Selective Excitation Studies of Unimolecular Reaction Dynamics Crim, F. F. Annual Review of Physical Chemistry, Vol. 35, Issue 1 https://doi.org/10.1146/annurev.pc.35.100184.003301	journal	October 1984
Let there be white light: supercontinuum generation by ultrashort laser pulses Zheltikov, Aleksei M. Uspekhi Fizicheskih Nauk, Vol. 176, Issue 6 https://doi.org/10.3367/UFNr.0176.200606d.0623	journal	January 2006

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