Is solvated trans-azobenzene twisted or planar?

Briquet, Ludovic; Vercauteren, Daniel P.; Perpète, Éric A.; Jacquemin, Denis

doi:10.1016/j.cplett.2005.09.119

Cited by 54 publications

(56 citation statements)

References 23 publications

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“…In addition, the difference with respect to the position of the first π → π absorption band of azobenzene (see Ref. [39] and reference therein), is nicely reproduced by TD-DFT: 0.85 eV with PBE0 versus 0.93 eV experimentally. For the meta and para di-azo dyes, theory undershoots significantly the transition energies, though the difference between M-6 and M-7 (−0.26 eV experimentally) is satisfactorily foreseen by our computation scheme (−0.21 eV).…”

Section: Additional Dyesmentioning

confidence: 70%

Absorption spectra of recently synthesised organic dyes: A TD‐DFT study

Jacquemin

Preat

Perpète

et al. 2010

Int J of Quantum Chemistry

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ABSTRACT:We use a time-dependent density functional theory approach to investigate the absorption spectra of a panel of organic dyes synthesised and characterised during 2009. Several chemical modifications (solid-state packing, oxidation, variation of acidity…) are tackled, and both successes and failures of theory are highlighted and discussed. The obtained deviations are compared to the errors reported previously for traditional families of organic dyes.

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Section: Additional Dyesmentioning

confidence: 70%

Absorption spectra of recently synthesised organic dyes: A TD‐DFT study

Jacquemin

Preat

Perpète

et al. 2010

Int J of Quantum Chemistry

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“…Therefore, we have selected B3LYP for optimizing the ground-state geometries as it predicts central N N distances in significantly better agreement with gas-phase experiment, for unsubstituted AB [64], and between MP2 and MP4(SDQ) lengths for most molecules listed in Table I (For 2,4-OH-AB, the B3LYP estimate of the N N bond length is 1.275 Å, where PBE0's is 1.267 Å. ).…”

Section: Methodological Investigationmentioning

confidence: 96%

“…For AB, choosing an adequate basis set is not a trivial task, as the balance between diffuse and polarization functions has to be conserved to reach an accurate description of the ground-state geometry [20,64]. For instance, Kurita et al have shown that 6-31+G(d) yields an (incorrect) off-planar twist for unsubstituted AB at the MP2 level [65,66].…”

Section: Methodological Investigationmentioning

confidence: 97%

Absorption spectra of azobenzenes simulated with time‐dependent density functional theory

Jacquemin

Preat

Perpète

et al. 2011

Int J of Quantum Chemistry

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Using time-dependent density functional theory and the polarizable continuum model, we have simulated the absorption spectra of an extended series of azobenzene dyes. First, we have determined a theoretical level optimal for this important class of dyes, and it turned out that a C-PCM-CAM-B3LYP/6-311+G(d,p)// C-PCM-B3LYP/6-311G(d,p) approach represents an effective compromise between chemical accuracy and computational cost. In a second stage, we have compared the theoretical and experimental transition energies for 46 n → π and 141 π → π excitations. For the full set, that spans over a 302-565 nm domain, we obtained a mean absolute deviation of 13 nm (0.10 eV) and a linear correlation coefficient of 0.95, illustrating the accuracy of our approach, though some significant outliers pertained. In a last step, the ABSORPTION SPECTRA OF AZOBENZENES SIMULATED WITH TD-DFTimpact of several modifications, that is, trans/cis isomerization, variation of the acidity of the medium and azo/hydrazo tautomerism have been modeled with two functionals.

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“…The solvent effect is only moderate, yet in full agreement with recent findings. 42 The effect of the PCM environment on calculated UV-vis spectra is described in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Quantum Chemical Investigation of Thermal Cis-to-Trans Isomerization of Azobenzene Derivatives: Substituent Effects, Solvent Effects, and Comparison to Experimental Data

et al. 2009

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Quantum chemical calculations of various azobenzene (AB) derivatives have been carried out with the goal to describe the energetics and kinetics of their thermal cis f trans isomerization. The effects of substituents, in particular their type, number, and positioning, on activation energies have been systematically studied with the ultimate goal to tailor the switching process. Trends observed for mono-and disubstituted species are discussed. A polarizable continuum model is used to study, in an approximate fashion, the cis f trans isomerization of azobenzenes in solution. The nature of the transition state(s) and its dependence on substituents and the environment is discussed. In particular for push-pull azobenzenes, the reaction mechanism is found to change from inversion in nonpolar solvents to rotation in polar solvents. Concerning kinetics, calculations based on the Eyring transition state theory give usually reliable activation energies and enthalpies when compared to experimentally determined values. Also, trends in the resulting rate constants are correct. Other computed properties such as activation entropies and thus preexponential rate factors are in only moderate agreement with experiment.

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Is solvated trans-azobenzene twisted or planar?

Cited by 54 publications

References 23 publications

Absorption spectra of recently synthesised organic dyes: A TD‐DFT study

Absorption spectra of recently synthesised organic dyes: A TD‐DFT study

Absorption spectra of azobenzenes simulated with time‐dependent density functional theory

Quantum Chemical Investigation of Thermal Cis-to-Trans Isomerization of Azobenzene Derivatives: Substituent Effects, Solvent Effects, and Comparison to Experimental Data

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