Dynamics of an excitation-transfer trimer: Interference, coherence, Berry's phase development, and vibrational control of non-adiabaticity

We detail several interesting features in the dynamics of an equilaterally shaped electronic excitation-transfer (EET) trimer with distance-dependent intermonomer excitation-transfer couplings. In the absence of electronic-vibrational coupling, symmetric and antisymmetric superpositions of two single-monomer excitations are shown to exhibit purely constructive, oscillatory, and purely destructive interference in the EET to the third monomer, respectively. In the former case, the transfer is modulated by motion in the symmetrical framework-expansion vibration induced by the Franck-Condon excitation. Distortions in the shape of the triangular framework degrade that coherent EET while activating excitation transfer in the latter case of an antisymmetric initial state. In its symmetrical configuration, two of the three single-exciton states of the trimer are degenerate. This degeneracy is broken by the Jahn-Teller-active framework distortions. The calculations illustrate closed, approximately circular pseudo-rotational wave-packet dynamics on both the lower and the upper adiabatic potential energy surfaces of the degenerate manifold, which lead to the acquisition after one cycle of physically meaningful geometric (Berry) phases of p. Another manifestation of Berry-phase development is seen in the evolution of the vibrational probability density of a wave packet on the lower Jahn-Teller adiabatic potential comprising a superposition of clockwise and counterclockwise circular motions. The circular pseudo-rotation on the upper cone is shown to stabilize the adiabatic electronic state against non-adiabatic internal conversion via the conical intersection, a dynamical process analogous to Slonczewski resonance. Strategies for initiating and monitoring these various dynamical processes experimentally using pre-resonant impulsive Raman excitation, short-pulse absorption, and multi-dimensional wave-packet interferometry are outlined in brief.

Automated summary

This article investigates the dynamics of an equilaterally shaped electronic excitation-transfer (EET) trimer with distance-dependent intermonomer excitation-transfer couplings. It is found that symmetric and antisymmetric superpositions of two single-monomer excitations exhibit different interferences in the EET to the third monomer. The shape distortion of the triangular framework affects the coherent EET and activates excitation transfer in the antisymmetric initial state. The study also reveals the significance of Jahn-Teller-active framework distortions in breaking the degeneracy of the trimer's single-exciton states.