Detecting Electronic Coherence by Multidimensional Broadband Stimulated X-Ray Raman Signals

TL;DR

This paper introduces multiple stimulated-Raman detection schemes using broadband X-ray pulses to monitor phase-sensitive electronic and nuclear dynamics in nonstationary molecular states, enhancing understanding of electronic coherences.

Contribution

It proposes and compares several novel X-ray stimulated-Raman detection protocols, including their linear and quadratic variants, for observing electronic coherences in molecules.

Findings

Different detection schemes provide distinct gating windows.

Off-resonant and resonant signals offer complementary information.

The methods enable phase-sensitive monitoring of electronic and nuclear dynamics.

Abstract

Nonstationary molecular states which contain electronic coherences can be impulsively created and manipulated by using recently-developed ultrashort optical and X-ray pulses via photoexcitation, photoionization and Auger processes. We propose several stimulated-Raman detection schemes that can monitor the phase-sensitive electronic and nuclear dynamics. Three detection protocols of an X-ray broadband probe are compared - frequency dispersed transmission, integrated photon number change, and total pulse energy change. In addition each can be either linear or quadratic in the X-ray probe intensity. These various signals offer different gating windows into the molecular response which is described by correlation functions of electronic polarizabilities. Off-resonant and resonant signals are compared.