Vibrational coherences in half-broadband 2D electronic spectroscopy: spectral filtering to identify excited state displacements

TL;DR

This paper explores how spectral filtering in half-broadband 2D electronic spectroscopy can clarify vibrational coherences and excited state displacements, emphasizing the importance of pump spectrum positioning for accurate interpretation.

Contribution

It demonstrates the impact of pump spectral positioning on resolving excited state vibrational coherences in half-broadband 2DES using a model based on cresyl violet.

Findings

Careful pump spectrum positioning enhances vibrational coherence resolution.

Spectral filtering aids in interpreting excited state displacements.

Caution is needed regarding spectral window effects in spectra analysis.

Abstract

Vibrational coherences in ultrafast pump-probe (PP) and 2D electronic spectroscopy (2DES) provide insight into the excited state dynamics of molecules. Femtosecond coherence spectra (FCS) and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES (HB2DES) uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. Careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. The paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra.