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

Sissaoui, Jihad; Budkina, Darya S.; Vauthey, Eric

doi:10.1021/acs.jpclett.3c01038

Cited by 6 publications

(12 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additionally, our analysis demonstrates that the dominant factor responsible for the symmetry breaking of CV and the resulting splitting of S 1 and S 2 peaks in methanol is the non-covalent interaction between the CV and the solvent environment rather than torsional disorder, in contrast to the results presented in a recent study. 8 In nonpolar solvents, we find that CV preferentially forms a contact ion configuration with Cl − , leading to strong symmetry breaking and a substantially larger S 1 -S 2 splitting than in methanol. Interestingly, our results demonstrate that the chromophore-ion configurations sampled during the MD in toluene, where the Cl − is preferentially located equidistant between two N atoms, are qualitatively different to the configurations sampled in vacuum, where the Cl − is more preferentially associated with a single N .…”

Section: Discussionmentioning

confidence: 74%

“…4 demonstrate that the S 1 -S 2 peak splitting of the absorption spectrum of CV in methanol is largely driven by symmetry breaking induced through electrostatic interactions with the polar solvent environment around the molecule, rather than symmetry breaking due to solvent-induced slow chromophore motion driven by the twisting of the aryl rings, in contrast with the results presented in a recent study. 8…”

Section: B the Absorption Spectrum Of CV In Methanolmentioning

confidence: 99%

“…2 The nature of the higher energy peak has been debated for decades and remains uncertain. [1][2][3][4][5][6][7][8] There are two main theories describing this phenomenon: 1) the ground state of CV is inhomogeneous and this causes the appearance of the second peak in absorption lineshape; or 2) solute-solvent interactions induce the D 3 symmetry of CV to break and cause the lifting of the degeneracy of the excited state. For instance, Lewis et al suggested the idea that in a solvent there is a thermal equilibrium between two isomers of CV 1 one of those is symmetrical helical type (D 3 symmetry) and the other one is distorted helical type (C 2 symmetry).…”

Section: Introductionmentioning

confidence: 99%

“…6 The most recent studies either do not support both theories, 7 or suggest that the center of the absorption band of CV corresponds to the excitation of the symmetric molecule, and the edges correspond to the S 1 and S 2 transitions of the symmetry-broken molecules according to QM calculations and time-resolved polarized spectroscopy data. 8 Thus, the dominant factor in the appearance of a shoulder in absorption spectrum of CV remains unclear, and can be ascribed to either the existence of two isomers of the ground state, torsional disorder of the molecule, environmental interactions, or a combination of these factors.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

First-principles Modeling of the Absorption spectrum of Crystal Violet in Solution - The Importance of Environmentally-driven Symmetry Breaking

Bashirova,

Zuehlsdorff

2024

Preprint

View full text Add to dashboard Cite

Theoretical spectroscopy plays a crucial role in understanding the properties of materials and molecules. One of the most promising methods for computing optical spectra of chromophores embedded in complex environments from the first principles is the cumulant approach, where both (generally anharmonic) vibrational degrees of freedom and environmental interactions are explicitly accounted for. In this work, we verify the capabilities of the cumulant approach in describing the effect of complex environmental interactions on linear absorption spectra by studying Crystal Violet (CV) in different solvents. The experimental absorption spectrum of CV strongly depends on the nature of the solvent, indicating strong coupling to the condensed-phase environment. We demonstrate that these changes in absorption lineshape are driven by an increased splitting between absorption bands of two low-lying excited states that is caused by a breaking of the D3 symmetry of the molecule, and that in polar solvents this symmetry-breaking is mainly driven by electrostatic interactions with the condensed phase environment, rather than distortion of the structure of the molecule, in contrast with conclusions reached in a number of previous studies. Our results reveal the importance explicitly including a counterion in the calculations in nonpolar solvent due to electrostatic interactions between CV and the ion. In polar solvent, these interactions are strongly reduced due to solvent screening effects, thus minimizing the symmetry breaking. Computed spectra in methanol are found to be in reasonable agreement with experiment, demonstrating the strengths of the outlined approach in modeling strong environmental interactions.

show abstract

Section: Discussionmentioning

confidence: 74%

Section: B the Absorption Spectrum Of CV In Methanolmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

First-principles Modeling of the Absorption spectrum of Crystal Violet in Solution - The Importance of Environmentally-driven Symmetry Breaking

Bashirova,

Zuehlsdorff

2024

Preprint

View full text Add to dashboard Cite

show abstract

“…Brilliant green showed the absorption maximum at 624 nm, with a sharp decrease in peak intensity within 2 h. Crystal violet shows the main absorption peak with a high-energy shoulder peak between 550 and 600 nm. 51 , 52 A sharp decrease in the intensity of the peak maxima after 2 h was observed. The interfacial interaction of crystal violet at the silica–water interface was measured in real time, 53 which suggested that CV can behave in the solution in two ways.…”

Section: Resultsmentioning

confidence: 89%

A Sustainable and Regenerative Process for the Treatment of Textile Effluents Using Nonphotocatalytic Water Splitting by Nanoporous Oxygen-Deficient Ferrite

Shukla,

Shah,

Badola

et al. 2024

ACS Omega

View full text Add to dashboard Cite

Water is crucial for life. Being the world's third-largest industry, the textile industry pollutes 93 billion cubic meters of water each year. Only 28% of textile wastewater is treated by lower-to middle-income countries due to the costly treatment methods. The present work demonstrates the utilization of surface oxygen defects and nanopores in Mg 0.8 Li 0.2 Fe 2 O 4 (Li-MgF) to treat textile effluents by a highly economical, scalable, and eco-friendly process. Nanoporous, oxygen-deficient Li-MgF splits water by a nonphotocatalytic process at room temperature to produce green electricity as hydroelectric cell. The adsorbent Li-MgF can be easily regenerated by heat treatment. A 70−90% reduction in the UV absorption intensity of adsorbent-treated textile effluents was observed by UV− visible spectroscopy. The oxygen defects on Li-MgF surface and nanopores were confirmed by X-ray photoelectron spectroscopy and Brunauer−Emmett−Teller (BET) measurements, respectively. To analyze the adsorption mechanism, three known organic water-soluble dyes, brilliant green, crystal violet, and congo red, were treated with nanoporous Li-MgF. The dye decolorization efficiency of Li-MgF was recorded to be 99.84, 99.27, and 99.31% at 250 μM concentrations of brilliant green, congo red, and crystal violet, respectively. The results of Fourier transform infrared (FTIR) spectroscopy confirmed the presence of dyes on the material surface attached through hydroxyl groups generated by water splitting on the surface of the material. Total organic carbon analysis confirmed the removal of organic carbon from the dye solutions by 82.8, 77.0, and 46.5% for brilliant green, Congo red, and crystal violet, respectively. Based on the kinetic and isotherm models, the presence of a large number of surface hydroxyl groups on the surface of the material and OH − ions in solutions generated by water splitting was found to be responsible for the complete decolorization of all of the dyes. Adsorption of chemically diverse dyes by the nanoporous, eco-friendly, ferromagnetic, economic, and reusable Li-MgF provides a sustainable and easy way to treat textile industry effluents in large amounts.

show abstract

First-Principles Modeling of the Absorption Spectrum of Crystal Violet in Solution: The Importance of Environmentally Driven Symmetry Breaking

Bashirova,

Zuehlsdorff

2024

J. Phys. Chem. A

View full text Add to dashboard Cite

Theoretical spectroscopy plays a crucial role in understanding the properties of the materials and molecules. One of the most promising methods for computing optical spectra of chromophores embedded in complex environments from the first principles is the cumulant approach, where both (generally anharmonic) vibrational degrees of freedom and environmental interactions are explicitly accounted for. In this work, we verify the capabilities of the cumulant approach in describing the effect of complex environmental interactions on linear absorption spectra by studying Crystal Violet (CV) in different solvents. The experimental absorption spectrum of CV strongly depends on the nature of the solvent, indicating strong coupling to the condensed-phase environment. We demonstrate that these changes in absorption line shape are driven by an increased splitting between absorption bands of two low-lying excited states that is caused by a breaking of the D 3 symmetry of the molecule and that in polar solvents, this symmetry breaking is mainly driven by electrostatic interactions with the condensed-phase environment rather than distortion of the structure of the molecule, in contrast with conclusions reached in a number of previous studies. Our results reveal the importance of explicitly including a counterion in the calculations in nonpolar solvents due to electrostatic interactions between CV and the ion. In polar solvents, these interactions are strongly reduced due to solvent screening effects, thus minimizing the symmetry breaking. Computed spectra in methanol are found to be in reasonable agreement with the experiment, demonstrating the strengths of the outlined approach in modeling strong environmental interactions.

show abstract

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

Cited by 6 publications

References 34 publications

First-principles Modeling of the Absorption spectrum of Crystal Violet in Solution - The Importance of Environmentally-driven Symmetry Breaking

First-principles Modeling of the Absorption spectrum of Crystal Violet in Solution - The Importance of Environmentally-driven Symmetry Breaking

A Sustainable and Regenerative Process for the Treatment of Textile Effluents Using Nonphotocatalytic Water Splitting by Nanoporous Oxygen-Deficient Ferrite

First-Principles Modeling of the Absorption Spectrum of Crystal Violet in Solution: The Importance of Environmentally Driven Symmetry Breaking

Contact Info

Product

Resources

About