Polariton chemistry: molecules in optical cavities
Joel Yuen-Zhou
University of California San Diego, Department of Chemistry and Biochemistry, 9500 Gilman Dr MC 0340, La Jolla, CA 92093, United States
Organic molecules interact strongly with confined electromagnetic fields in plasmonic arrays or optical microcavities owing to their bright transition dipole moments. This interaction gives rise to molecular polaritons, hybrid light-matter quasiparticles. Molecular polaritonics opens doors for new room-temperature opportunities for the nontrivial control of physico-chemical properties of molecular assemblies [1]. In this talk, I’ll showcase some of these opportunities that we have been theoretically (and, together with our experimental collaborators) exploring in the past few years. I will briefly discuss the relevant time and energy scales associated with molecular polaritons [1,2] and strategies to exploit them to control photoexcited processes including singlet fission [3], triplet harvesting [4], remote and topologically-protected energy transfer [5-7], and anomalous nonlinear optical effects [8,9]. Finally, I will conclude by explaining how vibrational polaritons can steer ground-state chemical reactions even in the absence of optical pumping [10], or be used to realize exotic processes such as remote control of chemical reactions [11].
REFERENCES
[1] R. F. Ribeiro, L. Martínez-Martínez, M. Du, and J. Yuen-Zhou, Polariton chemistry: controlling molecular dynamics with optical cavities, Chem. Sci. 9, 6325-6339 (2018).
[2] L. A. Martínez-Martínez, R. F. Ribeiro, J. A. Campos-González-Angulo, and J. Yuen-Zhou, Can ultrastrong coupling change ground-state chemical reactions?, ACS Photonics 5, 167 (2018).
[3] L. A. Martínez-Martínez, M. Du, R. F. Ribeiro, S. Kena-Cohen, and J. Yuen-Zhou, Polariton-assisted singlet fission in acene aggregates, J. Phys. Chem. Lett., 9, 1951-1957 (2018) (ACS editor’s choice).
[4] L. A. Martínez-Martínez, E. Eizner, R. F. Ribeiro, S. Kena-Cohen, and J. Yuen-Zhou, J. Chem. Phys. 151, 054106 (2019)
[5] M. Du, L. A. Martínez-Martínez, R. F. Ribeiro, Z. Hu, V. M. Menon, and J. Yuen-Zhou, Theory for polariton assisted remote energy transfer, Chem. Sci. 9, 6659-6669 (2018).
[6] J. Yuen-Zhou, S. K. Saikin, T. Zhu, M. Onbalsi, C. Ross, V. Bulovic, and M. Baldo, Plexcitons: Dirac points and topological modes, Nat. Commun. 7, 11783 (2016).
[7] J. Yuen-Zhou, S. Saikin, N. Yao, and A. Aspuru-Guzik, Topologically protected excitons in porphyrin thin films, Nature Mater. 13, 1026 (2014).
[8] B. Xiang, R. F. Ribeiro, A. D. Dunkelberger, J. Wang, Y. Li, B. S. Simpkins, J. C. Owrutsky, J. Yuen-Zhou, W. Xiong, Two-dimensional spectroscopy of vibrational polaritons, Proc. Nat. Acad. Sci. 201722063 (2018).
[9] R. F. Ribeiro, A. D. Dunkelberger, B. Xiang, W. Xiong, B. S. Simpkins, J. C. Owrutsky, J. Yuen-Zhou, Theory for nonlinear spectroscopy of vibrational polaritons, J. Phys. Chem. Lett. 9, 13, 3766--3771 (2018).
[10] J. Campos-González-Angulo, R. F. Ribeiro, and J. Yuen-Zhou, Resonant enhancement of thermally-activated reactions via vibrational polaritons, arXiV:1902.10264.
[11] M. Du, R. F. Ribeiro, L. A. Martínez-Martínez, and J. Yuen-Zhou, Remote control of chemistry in optical cavities, Chem 5, 5, 1167 (2019). (May 2019 journal cover).
