Generalized resonance energy transfer theory: Applications to vibrational energy flow in optical cavities

Abstract

A general rate theory for resonance energy transfer is formulated to incorporate any degrees of freedom (e.g., rotation, vibration, exciton, and polariton) as well as coherently-coupled composite states. The compact rate expression allows us to establish useful relationships: (i) detailed balance condition when the donor and acceptor are at the same temperature; (ii) proportionality to the overlap between donor's emission and acceptor's absorption spectra; (iii) scaling with the effective coherent size, i.e., the number of coherently coupled molecules; (iv) spatial and orientational dependences as derived from the interaction potential. When applied to cavity-assisted vibrational energy transfer, the rate formalism provides an intuitive and quantitative explanation of intriguing phenomena such as cooperativity, resonance, and nonlinearity in the collective vibrational strong coupling regime, as demonstrated in recent simulations.

Entangled biphoton enhanced double quantum coherence signal as a probe for cavity polariton correlations in presence of phonon induced dephasing

“…In a separate line of development, there have been a series of studies that have demonstrated the effective role of external electromagnetic cavities in manipulating material excitations. These studies range from the control of electronic excitations [7][8][9][10][11][12][13][14][15][16], vibrational modes [17,18], collective mode responses [19,20] to the cavity mode-assisted modulation of dynamical resonances [21][22][23][24][25]. Cavity mode interacting resonantly with narrow-band of excitons and off-resonantly with the rest may modulate the excitation dispersal by tuning the delocalization properties and influence the dephasing properties via the spectral weight modulation [26][27][28].…”

Entangled Biphoton Enhanced Double Quantum Coherence Signal as a Probe for Cavity Polariton Correlations in Presence of Phonon Induced Dephasing

“…In a separate line of development, there have been a series of studies that have demonstrated the effective role of external electromagnetic cavities in manipulating material excitations. These studies range from the control of electronic excitations [7][8][9][10][11][12][13][14][15][16], vibrational modes [17,18], collective mode responses [19,20] to the cavity mode-assisted modulation of dynamical resonances [21][22][23][24][25]. Cavity mode interacting resonantly with narrow-band of excitons and off-resonantly with the rest may modulate the excitation dispersal by tuning the delocalization properties and influence the dephasing properties via the spectral weight modulation [26][27][28].…”

Collective response in light-matter interactions: The interplay between strong coupling and local dynamics

“…Theoretical understanding of these observations is at present incomplete. Observed chemical consequences of vibrational strong coupling in the electronic ground state and in the absence of incident light still await theoretical descriptions despite recent efforts [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57].…”