Quantifying Robustness of Attosecond Transient Absorption Spectroscopy for Vibronic Coherence in Charge Migration

TL;DR

This paper develops a comprehensive theoretical framework for attosecond transient absorption spectroscopy (ATAS), demonstrating its ability to probe vibronic coherence in molecules and quantifying its robustness through a new coherence contrast factor.

Contribution

The work introduces a detailed theory for ATAS that includes orientation dependence and applies it to N₂⁺, revealing vibronic coherence signatures previously thought absent and establishing a measure for robustness.

Findings

Simulated spectra show clear vibronic coherence signatures in N₂⁺.

A coherence contrast factor quantifies ATAS robustness.

The theory advances understanding of ATAS in monitoring electronic motion.

Abstract

Probing vibronic coherence in molecules has been a central topic in ultrafast science, as it is an essential prerequisite to monitoring electronic motion. While experiments have demonstrated that attosecond transient absorption spectroscopy (ATAS) can probe the vibronic coherence in a few molecules, its robustness remains largely unexplored. In this Letter, we develop a comprehensive theory for ATAS which accounts for the orientation dependence of the density matrix of a pumped molecule. We apply our theory to N$_2^+$ formed by multiorbital tunnel ionization under a few-cycle intense near-infrared laser pulse. The simulated x-ray absorption spectrum shows clear signatures of the vibronic coherence between the $A^2\Pi_u$ and $B^2\Sigma_u^+$ states of N$_2^+$, which was predicted to be absent by a previous theory. We further define a coherence contrast factor to quantify the robustness of ATAS. This work advances the theoretical foundation of ATAS and paves the way for monitoring electronic motion in generic molecules.