On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge-Transfer Complexation

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2020 Mar 29

PMID 32220038

Citations 18

Authors

Yantao Pang

Anoop Thomas

Kalaivanan Nagarajan

Robrecht M A Vergauwe

Kripa Joseph

Bianca Patrahau

Kuidong Wang

Cyriaque Genet

Thomas W Ebbesen

Affiliations

Soon will be listed here.

Abstract

It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge-transfer (CT) complexation reaction. By studying the trimethylated-benzene-I CT complex, we find that VSC induces large changes in the equilibrium constant K of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.

Citing Articles

Subradiant plasmonic cavities make bright polariton states dark.

Yim J, Brawley Z, Sheldon M Nanophotonics. 2024; 13(11):2035-2045.

PMID: 39635085 PMC: 11501913. DOI: 10.1515/nanoph-2024-0058.

Measuring Kinetics under Vibrational Strong Coupling: Testing for a Change in the Nucleophilicity of Water and Alcohols.

Muller C, Mayer R, Piejko M, Patrahau B, Bauer V, Moran J Angew Chem Int Ed Engl. 2024; 63(49):e202410770.

PMID: 39167048 PMC: 11586696. DOI: 10.1002/anie.202410770.

Consequences of Vibrational Strong Coupling on Supramolecular Polymerization of Porphyrins.

Joseph K, de Waal B, Jansen S, van der Tol J, Vantomme G, Meijer E J Am Chem Soc. 2024; 146(17):12130-12137.

PMID: 38642054 PMC: 11066862. DOI: 10.1021/jacs.4c02267.

Molecular Polaritons for Chemistry, Photonics and Quantum Technologies.

Xiang B, Xiong W Chem Rev. 2024; 124(5):2512-2552.

PMID: 38416701 PMC: 10941193. DOI: 10.1021/acs.chemrev.3c00662.

Collective Strong Coupling Modifies Aggregation and Solvation.

Castagnola M, Haugland T, Ronca E, Koch H, Schafer C J Phys Chem Lett. 2024; 15(5):1428-1434.

PMID: 38290530 PMC: 10860139. DOI: 10.1021/acs.jpclett.3c03506.

References

Ebbesen T . Hybrid Light-Matter States in a Molecular and Material Science Perspective. Acc Chem Res. 2016; 49(11):2403-2412. DOI: 10.1021/acs.accounts.6b00295. View

Bakulin A, Lovrincic R, Yu X, Selig O, Bakker H, Rezus Y . Mode-selective vibrational modulation of charge transport in organic electronic devices. Nat Commun. 2015; 6:7880. PMC: 4538862. DOI: 10.1038/ncomms8880. View

Munkhbat B, Wersall M, Baranov D, Antosiewicz T, Shegai T . Suppression of photo-oxidation of organic chromophores by strong coupling to plasmonic nanoantennas. Sci Adv. 2018; 4(7):eaas9552. PMC: 6035039. DOI: 10.1126/sciadv.aas9552. View

Lin Z, Lawrence C, Xiao D, Kireev V, Skourtis S, Sessler J . Modulating unimolecular charge transfer by exciting bridge vibrations. J Am Chem Soc. 2009; 131(50):18060-2. DOI: 10.1021/ja907041t. View

Herrera F, Spano F . Cavity-Controlled Chemistry in Molecular Ensembles. Phys Rev Lett. 2016; 116(23):238301. DOI: 10.1103/PhysRevLett.116.238301. View

Wang S, Chervy T, George J, Hutchison J, Genet C, Ebbesen T . Quantum Yield of Polariton Emission from Hybrid Light-Matter States. J Phys Chem Lett. 2015; 5(8):1433-9. DOI: 10.1021/jz5004439. View

Lather J, Bhatt P, Thomas A, Ebbesen T, George J . Cavity Catalysis by Cooperative Vibrational Strong Coupling of Reactant and Solvent Molecules. Angew Chem Int Ed Engl. 2019; 58(31):10635-10638. PMC: 6771697. DOI: 10.1002/anie.201905407. View

Orgiu E, George J, Hutchison J, Devaux E, Dayen J, Doudin B . Conductivity in organic semiconductors hybridized with the vacuum field. Nat Mater. 2015; 14(11):1123-9. DOI: 10.1038/nmat4392. View

Vergauwe R, Thomas A, Nagarajan K, Shalabney A, George J, Chervy T . Modification of Enzyme Activity by Vibrational Strong Coupling of Water. Angew Chem Int Ed Engl. 2019; 58(43):15324-15328. PMC: 6856831. DOI: 10.1002/anie.201908876. View

10.

Flick J, Schafer C, Ruggenthaler M, Appel H, Rubio A . Ab Initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground State. ACS Photonics. 2018; 5(3):992-1005. PMC: 5865078. DOI: 10.1021/acsphotonics.7b01279. View

11.

Thomas A, Lethuillier-Karl L, Nagarajan K, Vergauwe R, George J, Chervy T . Tilting a ground-state reactivity landscape by vibrational strong coupling. Science. 2019; 363(6427):615-619. DOI: 10.1126/science.aau7742. View

12.

Zare . Laser control of chemical reactions . Science. 1998; 279(5358):1875-9. DOI: 10.1126/science.279.5358.1875. View

13.

Schafer C, Ruggenthaler M, Appel H, Rubio A . Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry. Proc Natl Acad Sci U S A. 2019; 116(11):4883-4892. PMC: 6421448. DOI: 10.1073/pnas.1814178116. View

14.

Zhong X, Chervy T, Zhang L, Thomas A, George J, Genet C . Energy Transfer between Spatially Separated Entangled Molecules. Angew Chem Int Ed Engl. 2017; 56(31):9034-9038. PMC: 5575472. DOI: 10.1002/anie.201703539. View

15.

Hirai K, Takeda R, Hutchison J, Uji-I H . Modulation of Prins Cyclization by Vibrational Strong Coupling. Angew Chem Int Ed Engl. 2020; 59(13):5332-5335. DOI: 10.1002/anie.201915632. View

16.

Hutchison J, Schwartz T, Genet C, Devaux E, Ebbesen T . Modifying chemical landscapes by coupling to vacuum fields. Angew Chem Int Ed Engl. 2012; 51(7):1592-6. DOI: 10.1002/anie.201107033. View

17.

Groenhof G, Toppari J . Coherent Light Harvesting through Strong Coupling to Confined Light. J Phys Chem Lett. 2018; 9(17):4848-4851. PMC: 6129961. DOI: 10.1021/acs.jpclett.8b02032. View

18.

Campos-Gonzalez-Angulo J, Ribeiro R, Yuen-Zhou J . Resonant catalysis of thermally activated chemical reactions with vibrational polaritons. Nat Commun. 2019; 10(1):4685. PMC: 6794294. DOI: 10.1038/s41467-019-12636-1. View

19.

Hagenmuller D, Schachenmayer J, Schutz S, Genes C, Pupillo G . Cavity-Enhanced Transport of Charge. Phys Rev Lett. 2017; 119(22):223601. DOI: 10.1103/PhysRevLett.119.223601. View

20.

Galego J, Garcia-Vidal F, Feist J . Many-Molecule Reaction Triggered by a Single Photon in Polaritonic Chemistry. Phys Rev Lett. 2018; 119(13):136001. DOI: 10.1103/PhysRevLett.119.136001. View