Vibrational and electronic spectra of benzophenone in different phase states: Ab initio calculations and experiment

Bezrodna, T.; Mel'nik, V. I.; Puchkovskaya, G. A.; Savranskii, L. I.

doi:10.1007/s10947-006-0286-8

Cited by 7 publications

(11 citation statements)

References 8 publications

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“…Its maximum extension comes to 1.1 eV, compared to the threshold at 1.5 eV. 13 This shift can be due to Franck-Condon excitation of high vibrational levels of the intermediate level as depicted in Fig. 12 through S n and this vibrational excitation is transposed into the ion levels causing the shift.…”

Section: Monitoring the Evolution With Photoelectron Spectramentioning

confidence: 96%

“…Strong coupling results from a quasi resonant T 2 (pp*) state with S 1 (np*). 30,35 Such a T 2 (pp*) state has been calculated 13 and is degenerate with S 1 . However the delocalisation of the p* orbital over the benzophenone molecule is only possible in the planar case, from which the benzophenone molecule deviates by a B301 torsion for each benzene cycle.…”

Section: S 1 -T 1 Intersystem Crossingmentioning

confidence: 99%

“…10,11 The lowest triplet, T(np*), is expected at 24 044 cm À1 in the gas phase, from the 2200 cm À1 S-T splitting in cryogenic crystals. 12 The second lowest triplet state is believed to be of pp* nature and is calculated at 26 316 cm À1 , 13 in quasiresonance with S 1 . This resonance should drive a non-negligible spin-orbit coupling matrix element between S 1 (np*) and T 2 (pp*) along El Sayed rules.…”

Section: Introductionmentioning

confidence: 99%

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Gas phase dynamics of triplet formation in benzophenone

Spighi

Gaveau

Mestdagh

et al. 2014

Phys. Chem. Chem. Phys.

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Benzophenone is a prototype molecule for photochemistry in the triplet state through its high triplet yield and reactivity. We have investigated its dynamics of triplet formation under the isolated gas phase conditions via femtosecond and nanosecond time resolved photoelectron spectroscopy. This represents the complete evolution from the excitation in S2 to the final decay of T1 to the ground state S0. We have found that the triplet formation can be described almost as a direct process in preparing T1, the lowest reacting triplet state, from the S1 state after S2 → S1 internal conversion. The molecule was also deposited by a pick-up technique on cold argon clusters providing a soft relaxation medium without evaporation of the molecule and the mechanism was identical. This cluster technique is a model for medium influenced electronic relaxation and provides a continuous transition from the isolated gas phase to the relaxation dynamics in solution.

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Section: Monitoring the Evolution With Photoelectron Spectramentioning

confidence: 96%

Section: S 1 -T 1 Intersystem Crossingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Gas phase dynamics of triplet formation in benzophenone

Spighi

Gaveau

Mestdagh

et al. 2014

Phys. Chem. Chem. Phys.

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“…2− but also for the n-π* transitions of benzyl and benzophenone in (S,S)-2,3-butanediol ( Figure 1) [40]. The ICD effects for these aromatic groups were ascribed to the inherently twisting conformations of benzyl groups due to their H-H repulsion [41]. Further study on ICD effects has been reported by Hayward et al for the n-π* transitions of 10 symmetric and racemic aliphatic ketones in six chiral tetrahydrofuranols (Figure 1) [42].…”

Section: Induced Circular Dichroism For Small Moleculesmentioning

confidence: 97%

Chiral Solvation Induced Supramolecular Chiral Assembly of Achiral Polymers

Zhang¹,

Zhao²,

Yin³

2017

Molecular Self-Assembly in Nanoscience and Nanotechnology

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To date, liquid crystal chirality, mechanophysical chirality, circularly polarized photon chirality, gelation and chiral solvation are all feasible candidates to generate optically active polymers and supramolecular chirality when employing achiral molecules as starting substances. Among this, chiral-solvation-induced chirality is one of the dominant methods for construction of chirality from achiral sources, such as achiral poly(n-hexyl isocyanate) (PHIC), π-conjugated polymers, oligo(p-phenylenevinylene), polyacetylenes, σ-conjugated polysilanes and side-chain polymers. Supramolecular chirality is well established through their intra-or inter-molecular noncovalent interactions, such as van der Waals, CH/π, dipole-dipole interactions, hydrogen bonding and metal-ligand coordinating interactions. Compared with the traditional methods, this strategy avoids the use of expensive chiral reagents and also expands the scope towards challenging substrates. This chapter highlights a series of studies that include: (i) the development-historical background of chiral solvent induction strategy; (ii) the chiral-solvation-induced chirality in small molecules and oligomers; and (iii) recent developments in polymers, especially in π-conjugated polymers and σ-conjugated polymers.

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“…Mason et al [87] [88]. A recent vibrational experimental and ab initio theoretical study revealed that benzyl adopts an inherently twisting conformation due to the H-H repulsion [89]. Hayward et al [90] studied the ICD effects of ten aliphatic ketones (acyclics and cyclics) in six chiral tetrahydrofuranols (Figure 2).…”

Section: Optically-active Molecules In the Ground Statementioning

confidence: 99%

Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

Fujiki

2014

Symmetry

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Controlled mirror symmetry breaking arising from chemical and physical origin is currently one of the hottest issues in the field of supramolecular chirality. The dynamic twisting abilities of solvent molecules are often ignored and unknown, although the targeted molecules and polymers in a fluid solution are surrounded by solvent molecules. We should pay more attention to the facts that mostly all of the chemical and physical properties of these molecules and polymers in the ground and photoexcited states are significantly influenced by the surrounding solvent molecules with much conformational freedom through non-covalent supramolecular interactions between these substances and solvent molecules. This review highlights a series of studies that include: (i) historical background, covering chiral NaClO 3 crystallization in the presence of D-sugars in the late 19th century; (ii) early solvent chirality effects for optically inactive chromophores/fluorophores in the 1960s-1980s; and (iii) the recent development of mirror symmetry breaking from the corresponding achiral or optically inactive molecules and polymers with the help of molecular chirality as the solvent use quantity.

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Vibrational and electronic spectra of benzophenone in different phase states: Ab initio calculations and experiment

Cited by 7 publications

References 8 publications

Gas phase dynamics of triplet formation in benzophenone

Gas phase dynamics of triplet formation in benzophenone

Chiral Solvation Induced Supramolecular Chiral Assembly of Achiral Polymers

Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

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