Anisotropy factor spectra for weakly allowed electronic transitions in chiral ketones

TL;DR

This study combines quantum chemical calculations and experimental data to analyze anisotropy spectra of weakly allowed electronic transitions in chiral ketones, emphasizing the importance of non-Condon effects and vibrational contributions.

Contribution

It introduces a comprehensive theoretical model that incorporates Herzberg-Teller corrections and vibrational effects to accurately describe anisotropy spectra in chiral ketones.

Findings

Herzberg-Teller corrections are essential for matching experimental anisotropy data.

Vibrational degrees of freedom significantly influence electronic circular dichroism.

The model improves understanding of weakly allowed electronic transitions in chiral molecules.

Abstract

Quantum chemical calculations of one-photon absorption, electronic circular dichroism and anisotropy factor spectra for the A-band transition of fenchone, camphor and 3-methylcyclopentanone (3MCP) are reported. While the only weakly allowed nature of the transition leads to comparatively large anisotropies, a proper theoretical description of the absorption for such a transition requires to account for non-Condon effects. We present experimental data for the anisotropy of 3MCP in the liquid phase and show that corresponding Herzberg-Teller corrections are critical to reproduce the main experimental features. The results obtained with our comprehensive theoretical model highlight the importance of the vibrational degree of freedom, paving the way for a deeper understanding of the dynamics in electronic circular dichroism.