An experimental investigation of the effect of alkyl substituents on the position of the K and R absorption bands in acrolein derivatives

Moskvin, A. F.; Yablonskii, O. P.; Bondar, L. F.

doi:10.1007/bf01111990

Cited by 34 publications

(51 citation statements)

References 8 publications

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“…The obtained results are in excellent agreement with the previously reported experimental data. [44][45][46][47]49 Therefore, the gas-to-aqueous solution shift in the n → * absorption energy of acrolein is measured to be 0.25 eV.…”

Section: A Uv Spectroscopic Measurementsmentioning

confidence: 99%

“…50 The strongest → * absorption of acrolein in aqueous solution was observed at 5.90 eV. 47 Based on the experimental data reported in Ref. 47, the n → * absorption is blueshifted by 0.25 eV going from gas phase to a water solution, whereas the → * transition is strongly redshifted by −0.52 eV.…”

Section: Introductionmentioning

confidence: 99%

“…47 Based on the experimental data reported in Ref. 47, the n → * absorption is blueshifted by 0.25 eV going from gas phase to a water solution, whereas the → * transition is strongly redshifted by −0.52 eV. We note that n → * electronic absorption band is seen to be slightly blueshifted even in apolar solvents, e.g., by 0.01, 0.02, and 0.05 eV in isooctane, 47 n-hexane, 52 and 2-methyltetrahydrofuran 53 solutions, respectively, whereas the → * transition suffers a sizable gas-to-isooctane solution shift of −0.30 eV.…”

Section: Introductionmentioning

confidence: 99%

“…47, the n → * absorption is blueshifted by 0.25 eV going from gas phase to a water solution, whereas the → * transition is strongly redshifted by −0.52 eV. We note that n → * electronic absorption band is seen to be slightly blueshifted even in apolar solvents, e.g., by 0.01, 0.02, and 0.05 eV in isooctane, 47 n-hexane, 52 and 2-methyltetrahydrofuran 53 solutions, respectively, whereas the → * transition suffers a sizable gas-to-isooctane solution shift of −0.30 eV. 47 The latter observation indicates that the solvent shift in the electronic → * transition of acrolein is to some extent governed by intermolecular interactions of nonelectrostatic origin, and both electrostatic and nonelectrostatic intermolecular interactions tend to redshift the absorption maximum for this specific transition.…”

Section: Introductionmentioning

confidence: 99%

“…The n → * absorption of acrolein in the vapor phase exhibits a broad band between 3.20 and 5.00 eV, 44 with partially resolved vibronic structure, [44][45][46] and the maximum in the absorption intensity at 3.69 eV. [44][45][46][47] In aqueous solution, the maximum intensity of this transition was observed in the region of 3.78-3.98 eV in Ref. 48 and at 3.94 eV in Refs.…”

Section: Introductionmentioning

confidence: 99%

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A subsystem density-functional theory approach for the quantum chemical treatment of proteins

Jacob

Visscher

2008

The Journal of Chemical Physics

136

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The performance of the Hartree-Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n → * and → * electronic excitation energies of acrolein. All electronic structure methods employed the same solvent model, which is based on the combined quantum mechanics/molecular mechanics approach together with a dynamical averaging scheme. In addition to the predicted solvatochromic effects, we have also performed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n → * excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the → * electronic transition in solution, whereas the recent CAM-B3LYP functional performs well also in this case. The → * excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental data.

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Section: A Uv Spectroscopic Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A subsystem density-functional theory approach for the quantum chemical treatment of proteins

Jacob

Visscher

2008

The Journal of Chemical Physics

136

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The Structure of Acrolein in a Liquid Crystal Phase

Celebre

Concistrè

et al. 2005

Chemistry A European J

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The (1)H NMR spectrum of a sample of acrolein dissolved in the nematic liquid crystal phase I52 has been analysed to yield 18 dipolar couplings between all the magnetic nuclei in the molecule; moreover, the (13)C and (13)C{(1)H} NMR spectra of a sample of acrolein in CDCl(3) were recorded and analysed to determine the indirect J(ij) couplings. The data were used to obtain the relative positions of the carbon and hydrogen atoms, assuming that these are independent of the conformations generated by rotation around the C--C bond through an angle phi, and to obtain a probability distribution P(phi). It has been found that in the liquid phase, the distribution is a maximum at the trans form whereas the abundance of the cis form is significantly smaller compared with that found by microwave spectroscopy or high level quantum mechanical calculations. Such calculations produced also a suitable force field needed to develop suitable strategies for vibrational correction procedure in the case of flexible molecules.

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A two‐scale approach to electron correlation in multiconfigurational perturbation theory

2014

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We present a new approach for the calculation of dynamic electron correlation effects in large molecular systems using multiconfigurational second-order perturbation theory (CASPT2). The method is restricted to cases where partitioning of the molecular system into an active site and an environment is meaningful. Only dynamic correlation effects derived from orbitals extending over the active site are included at the CASPT2 level of theory, whereas the correlation effects of the environment are retrieved at lower computational costs. For sufficiently large systems, the small errors introduced by this approximation are contrasted by the substantial savings in both storage and computational demands compared to the full CASPT2 calculation. Provided that static correlation effects are correctly taken into account for the whole system, the proposed scheme represent a hierarchical approach to the electron correlation problem, where two molecular scales are treated each by means of the most suitable level of theory.

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An experimental investigation of the effect of alkyl substituents on the position of the K and R absorption bands in acrolein derivatives

Cited by 34 publications

References 8 publications

A subsystem density-functional theory approach for the quantum chemical treatment of proteins

A subsystem density-functional theory approach for the quantum chemical treatment of proteins

The Structure of Acrolein in a Liquid Crystal Phase

A two‐scale approach to electron correlation in multiconfigurational perturbation theory

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