Coherence specific signal detection via chiral pump-probe spectroscopy

TL;DR

This paper proposes a theoretical method using transient circular dichroism spectroscopy with a specific pump-probe setup to isolate and detect quantum coherence dynamics in excitonic systems, minimizing ground state interference.

Contribution

It introduces a formalism to decompose TRCD signals into chiral and achiral components, enabling unambiguous detection of excited state coherence beating in pump-probe experiments.

Findings

Chiral doorway signals can be isolated by varying the angle θ.

Ground state contributions are weak and can be neglected with impulsive pumping.

Numerical simulations demonstrate the method's effectiveness in a dimer system.

Abstract

We examine transient circular dichroism spectroscopy (TRCD) as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle $\theta$ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of $\theta$. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system.