Vibrational Polaritonics: Nonlinear Optics and Prospects of Condensation

Microscopic ensembles of localized molecular vibrational transitions can strongly couple to infrared cavity modes giving rise to hybrid light-matter states known as vibrational polaritons. In this talk, I will briefly review the novel nonlinear optical processes that these systems can feature due to the interplay of long-range coherence of to the electromagnetic mode as well as the local anharmonic properties of the molecular vibrations. In particular, I will highlight how to leverage polariton and dark states to obtain an interesting toolkit of nonlinear ultrafast phenomena including Rabi splitting contraction [1], vibrational ladder climbing [2], and remote energy transfer [3,4]. I will also describe the possibilities of observing the onset of vibrational polariton condensation and what such a phenomenon would entail for control of chemical reactivity [5].<br/> <br/>[1] 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).<br/>[2] R. F. Ribeiro, J. A. Campos-González-Angulo, N. C. Giebink, W. Xiong, and J. Yuen-Zhou, Enhanced optical nonlinearities under strong light-matter coupling, Phys. Rev. A 103, 063111 (2021).<br/>[3] B. Xiang, R.F. Ribeiro, M. Du, L. Chen, Z. Yang, J. Wang, J. Yuen-Zhou, and W. Xiong, Intermolecular vibrational energy transfer enabled by microcavity strong light-matter coupling, Science 368, 6491 (2020).<br/>[4] 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).<br/>[5] S. Pannir-sivajothi, J. A. Campos-Gonzalez-Angulo, L. A. Martínez-Martínez, S. Sinha, and J. Yuen-Zhou, Driving chemical reactions with polariton condensates, Nat. Commun. 13, 1645 (2022).