Theoretical analysis of charge-transfer electronic spectra of methylated benzenes—TCNE complexes including solvent effects: approaching experiment

Mach, Pavel; Budzák, Šimon; Medveď, Miroslav; Kyseľ, O.

doi:10.1007/s00214-012-1268-x

Cited by 11 publications

(19 citation statements)

References 70 publications

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“…These stacked-type conformations were also used in previous theoretical investigations. 3,[54][55][56][57] The TCNE molecule is located over the middle portion of the aromatic ring. In Scheme 1 the four investigated structures, including the two arrangements of the anthracene-TCNE complex, are displayed.…”

Section: Resultsmentioning

confidence: 99%

“…These excited states have been intensively investigated by means of experimental 52,53 and theoretical methods. 3,21,24,[54][55][56][57][58][59] Furthermore, aromatic hydrocarbon-TCNE complexes are also considered as important benchmark systems to assess the ability of different theoretical approaches to describe intermolecular interactions 14 and CT transitions. 3,21,24,[54][55][56][57][58][59] Because these aromatic-TCNE complexes are significantly smaller as compared to realistic donor-acceptor boundary structures (e.g., PTB1-PCBM), 42 they also provide an excellent testing ground for different theoretical methods, 3,24,58 in particular for the ADC(2) method used in the present work.…”

Section: Introductionmentioning

confidence: 99%

“…Mach and co-workers used CC2, TD-DFT and CIS methods to compute the electronic excitations in TCNE complexes. 56,57 To our knowledge, no quantum chemical calculations on solvatochromic effects for the aromatic hydrocarbon-TCNE complexes have been performed.…”

Section: Introductionmentioning

confidence: 99%

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Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon–tetracyanoethylene complexes

Aquino

Borges

Nieman

et al. 2014

Phys. Chem. Chem. Phys.

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A comprehensive theoretical study of the electronically excited states in complexes between tetracyanoethylene (TCNE) and three aromatic electron donors, benzene, naphthalene and anthracene, was performed with a focus on charge transfer (CT) transitions. The results show that the algebraic diagrammatic construction method to second order (ADC(2)) provides excellent possibilities for reliable calculations of CT states. Significant improvements in the accuracy of the computed transition energies are obtained by using the scaled opposite-spin (SOS) variant of ADC(2). Solvent effects were examined on the basis of the conductor-like screening model (COSMO) which has been implemented recently in the ADC(2) method. The dielectric constant and the refractive index of dichloromethane have been chosen in the COSMO calculations to compare with experimental solvatochromic effects. The computation of optimized ground state geometries and enthalpies of formation has been performed at the second-order Møller-Plesset perturbation theory (MP2) level. By comparison with experimental data and with high-level coupled-cluster methods including explicitly correlated (F12) wave functions, the importance of the SOS approach is demonstrated for the ground state as well. In the benzene-TCNE complex, the two lowest electronic excitations are of CT character whereas in the naphthalene and anthracene TCNE complexes three low-lying CT states are observed. As expected, they are strongly stabilized by the solvent. Geometry optimization in the lowest excited state allowed the calculation of fluorescence transitions. Solvent effects lead to a zero gap between S1 and S0 for the anthracene-TCNE complex. Therefore, in the series of benzene-TCNE to anthracene a change from a radiative to a nonradiative decay mechanism to the ground state is to be expected.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon–tetracyanoethylene complexes

Aquino

Borges

Nieman

et al. 2014

Phys. Chem. Chem. Phys.

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“…Recently, most CT investigations focussed on pinpointing an adequate hybrid (typically a RSH) . Nguyen and coworkers investigated 19 ES in donor‐acceptor complexes between TCE and aromatic compounds with a large panel of RSH and the cc‐pVDZ approach .…”

Section: Comparisons With Experimental Valuesmentioning

confidence: 99%

TD-DFT benchmarks: A review

Laurent

Jacquemin

2013

Int. J. Quantum Chem

1,074

961

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International audienceTime-Dependent Density Functional Theory (TD-DFT) has become the most widely-used theoretical approach to simulate the optical properties of both organic and inorganic molecules. In this contribution, we review TD-DFT benchmarks that have been performed during the last decade. The aim is often to pinpoint the most accurate or adequate exchange-correlation functional(s). We present both the different strategies used to assess the functionals and the main results obtained in terms of accuracy. In particular, we discuss both vertical and adiabatic benchmarks and comparisons with both experimental and theoretical reference transition energies. More specific benchmarks (oscillator strengths, excited-state geometries, dipole moments, vibronic shapes, etc.) are summarized as well. (c) 2013 Wiley Periodicals, Inc

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“…As a natural continuation, we decided to test the validity of our methodology, hereafter termed as MD–PMM, by studying one of the most investigated examples of CS–CR bimolecular reactions involving the photo-excitation of EDAC between an aromatic species (Ar) and tetracyanoethylene (TCNE) in solution, according to Scheme 1. 48–54…”

Section: Introductionmentioning

confidence: 99%

Theoretical-computational modeling of photo-induced charge separation spectra and charge recombination kinetics in solution

Piacente

Amadei

D’Abramo

et al. 2014

Phys. Chem. Chem. Phys.

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In this study we propose a theoretical-computational method, essentially based on molecular dynamics simulations and quantum-chemical calculations, for modelling the photo-induced charge separation (CS) and the subsequent charge recombination (CR) processes in solution. In particular we have reproduced the low-energy UV-Vis spectra of systems composed by an aromatic species (Ar = benzene or indene) and tetracyanoethylene (TCNE) in chloroform solution, dominated by the formation of the Ar(+)-TCNE(-) ion pair (IP) complex. The kinetics of the charge recombination process leading to the regeneration of Ar and TCNE has also been modelled. In both the cases the agreement with the experimental data is satisfactory. Although the presence of systematic deficiencies makes our approach unable to address some key aspects of the above processes (e.g. the ultrafast internal vibrational redistribution), it appears to be a rather promising tool for modelling the CS-CR process for atomic-molecular systems of very high complexity. The involvement of the triplet IP complex has also been discussed.

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Theoretical analysis of charge-transfer electronic spectra of methylated benzenes—TCNE complexes including solvent effects: approaching experiment

Cited by 11 publications

References 70 publications

Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon–tetracyanoethylene complexes

Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon–tetracyanoethylene complexes

TD-DFT benchmarks: A review

Theoretical-computational modeling of photo-induced charge separation spectra and charge recombination kinetics in solution

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