Utilizing Microcavities to Suppress Third-order Cascades in Fifth-order Raman Spectra

Abstract

Nonlinear optical signals in the condensed phase are often accompanied by sequences of lower-order processes, known as cascades, which share the same phase matching and power dependence on the incoming fields and are thus hard to distinguish. The suppression of cascading in order to reveal the desired nonlinear signal has been a major challenge in multidimensional Raman spectroscopy, i.e., the ${\chi }^{(5)}$ signal being masked by cascading signals given by a product of two ${\chi }^{(3)}$ processes. Since cascading originates from the exchange of a virtual photon between molecules, it can be manipulated by performing the experiment in an optical microcavity. Using a quantum electrodynamical (QED) treatment we demonstrate that the ${\chi }^{(3)}$ cascading contributions can be greatly suppressed. By optimizing the cavity size and the incoming pulse directions, we show that up to $\sim$99.5\% suppression of the cascading signal is possible.

arXiv comment15 pages, 2 figures; Accepted by J. Phys. Chem. Lett

References in corpus (8)

• Cavity-controlled chemistry in molecular ensembles
• Non-adiabatic dynamics of molecules in optical cavities
• Synchronization of Interacting Quantum Dipoles
• Quantum State and Process Tomography of Energy Transfer Systems via Ultrafast Spectroscopy
• Origin of long-lived coherence and excitation dynamics in pigment-protein complexes
• Cascading and Local-Field Effects in Non-Linear Optics Revisited; A Quantum-Field Picture Based on Exchange of Photons
• Nonequilibrium-induced enhancement of dynamical quantum coherence and entanglement of spin arrays
• Discriminating Cascading Processes in Nonlinear Optics; A QED Analysis Based on Their Molecular and Geometric Origin

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