Scientific article

Torsional Disorder, Symmetry Breaking, and the Crystal Violet Shoulder Controversy

Published inThe journal of physical chemistry letters, vol. 14, p. 5602-5606
Publication date2023-06-12
First online date2023-06-12

The nature of the lowest-energy electronic absorption band of crystal violet (CV) and particularly the origin of its high-energy shoulder have been debated since the middle of the past century. The most recent studies invoke a splitting of the S1 state upon symmetry breaking induced by interactions with the solvent and/or the counter-ion. Using a combination of stationary and time-resolved polarized spectroscopy together with quantum-chemical calculations, we show that torsional disorder in the ground-state results in an inhomogeneous broadening of the absorption band of CV. The center of the band is mostly due to symmetric molecules with a degenerate S1 state, whereas the edges originate from transitions to the S1 and S2 states of distorted symmetry-broken molecules. Transient-absorption measurements with different excitation wavelengths reveal that these two groups of molecules interconvert rapidly in liquid but not in a rigid environment.

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Citation (ISO format)
SISSAOUI, Jihad, BUDKINA, Darya S., VAUTHEY, Eric. Torsional Disorder, Symmetry Breaking, and the Crystal Violet Shoulder Controversy. In: The journal of physical chemistry letters, 2023, vol. 14, p. 5602–5606. doi: 10.1021/acs.jpclett.3c01038
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Article (Accepted version)
accessLevelRestrictedaccessLevelPublic 06/13/2024
Article (Published version)
ISSN of the journal1948-7185

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