Theory Predicts UV/vis-to-IR Photonic Down Conversion Mediated by Excited State Vibrational Polaritons

Overview

Journal Nat Commun

Specialty Biology

Date 2023 Aug 9

PMID 37558658

Authors

Connor K Terry Weatherly

Justin Provazza

Emily A Weiss

Roel Tempelaar

Affiliations

Soon will be listed here.

Abstract

This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are used to identify 1-Pyreneacetic acid as a molecule with this property and the dynamics of ESVP are modeled. Overall, this work introduces an avenue of polariton chemistry where excited state dynamics are influenced by the formation of vibrational polaritons. Along with this, the UV/vis-to-IR photonic down conversion is potentially useful in both sensing excited state vibrations and quantum transduction schemes.

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References

Schultz J, Shin J, Chen M, OConnor J, Young R, Ratner M . Influence of Vibronic Coupling on Ultrafast Singlet Fission in a Linear Terrylenediimide Dimer. J Am Chem Soc. 2021; 143(4):2049-2058. DOI: 10.1021/jacs.0c12201. View

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

Dunkelberger A, Spann B, Fears K, Simpkins B, Owrutsky J . Modified relaxation dynamics and coherent energy exchange in coupled vibration-cavity polaritons. Nat Commun. 2016; 7:13504. PMC: 5121416. DOI: 10.1038/ncomms13504. View

George J, Shalabney A, Hutchison J, Genet C, Ebbesen T . Liquid-Phase Vibrational Strong Coupling. J Phys Chem Lett. 2015; 6(6):1027-31. DOI: 10.1021/acs.jpclett.5b00204. View

Menghrajani K, Nash G, Barnes W . Vibrational Strong Coupling with Surface Plasmons and the Presence of Surface Plasmon Stop Bands. ACS Photonics. 2019; 6(8):2110-2116. PMC: 6711361. DOI: 10.1021/acsphotonics.9b00662. View

Szakacs Z, Vauthey E . Excited-State Symmetry Breaking and the Laporte Rule. J Phys Chem Lett. 2021; 12(16):4067-4071. DOI: 10.1021/acs.jpclett.1c00893. View

Dunkelberger A, Simpkins B, Vurgaftman I, Owrutsky J . Vibration-Cavity Polariton Chemistry and Dynamics. Annu Rev Phys Chem. 2022; 73:429-451. DOI: 10.1146/annurev-physchem-082620-014627. View

Flick J, Ruggenthaler M, Appel H, Rubio A . Atoms and molecules in cavities, from weak to strong coupling in quantum-electrodynamics (QED) chemistry. Proc Natl Acad Sci U S A. 2017; 114(12):3026-3034. PMC: 5373338. DOI: 10.1073/pnas.1615509114. View

Johnson P, Halpin A, Morizumi T, Prokhorenko V, Ernst O, Miller R . Local vibrational coherences drive the primary photochemistry of vision. Nat Chem. 2015; 7(12):980-6. DOI: 10.1038/nchem.2398. View

10.

Tiwari V, Peters W, Jonas D . Electronic resonance with anticorrelated pigment vibrations drives photosynthetic energy transfer outside the adiabatic framework. Proc Natl Acad Sci U S A. 2012; 110(4):1203-8. PMC: 3557059. DOI: 10.1073/pnas.1211157110. View

11.

Jonas D . Vibrational and Nonadiabatic Coherence in 2D Electronic Spectroscopy, the Jahn-Teller Effect, and Energy Transfer. Annu Rev Phys Chem. 2018; 69:327-352. DOI: 10.1146/annurev-physchem-052516-050602. View

12.

Wang Q, Schoenlein R, Peteanu L, Mathies R, Shank C . Vibrationally coherent photochemistry in the femtosecond primary event of vision. Science. 1994; 266(5184):422-4. DOI: 10.1126/science.7939680. View

13.

Nagarajan K, Thomas A, Ebbesen T . Chemistry under Vibrational Strong Coupling. J Am Chem Soc. 2021; 143(41):16877-16889. DOI: 10.1021/jacs.1c07420. View

14.

Womick J, Moran A . Vibronic enhancement of exciton sizes and energy transport in photosynthetic complexes. J Phys Chem B. 2011; 115(6):1347-56. DOI: 10.1021/jp106713q. View

15.

Mandal A, Montillo Vega S, Huo P . Polarized Fock States and the Dynamical Casimir Effect in Molecular Cavity Quantum Electrodynamics. J Phys Chem Lett. 2020; 11(21):9215-9223. DOI: 10.1021/acs.jpclett.0c02399. View

16.

Bakulin A, Morgan S, Kehoe T, Wilson M, Chin A, Zigmantas D . Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy. Nat Chem. 2015; 8(1):16-23. DOI: 10.1038/nchem.2371. View

17.

Fuller F, Pan J, Gelzinis A, Butkus V, Senlik S, Wilcox D . Vibronic coherence in oxygenic photosynthesis. Nat Chem. 2014; 6(8):706-11. DOI: 10.1038/nchem.2005. View

18.

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

19.

Monahan N, Sun D, Tamura H, Williams K, Xu B, Zhong Y . Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene. Nat Chem. 2017; 9(4):341-346. DOI: 10.1038/nchem.2665. View

20.

Duan H, Jha A, Li X, Tiwari V, Ye H, Nayak P . Intermolecular vibrations mediate ultrafast singlet fission. Sci Adv. 2020; 6(38). PMC: 7500928. DOI: 10.1126/sciadv.abb0052. View