Solvent effects on the electronic absorption spectrum of camphor using continuum, discrete or explicit approaches

Kongsted, Jacob; Mennucci, Benedetta; Coutinho, Kaline; Canuto, Sylvio

doi:10.1016/j.cplett.2009.11.026

Cited by 25 publications

(31 citation statements)

References 23 publications

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“…The use of the COSMO model (Fig. 4C) resulted in an average error of 9% due to the lack of explicit solvation [15,34,39]. The results obtained using the hybrid continuum/discrete description approach are in good agreement with experimental data (av.…”

Section: Quantum Mechanics: Vertical Electronic Transition Energies Asupporting

confidence: 86%

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Effect of solute flexibility and polarization on the solvatochromic shift of a brominated merocyanine dye in water: A sequential MD/QM study

Malaspina¹,

Fileti²,

Bastos³

2011

Int J of Quantum Chemistry

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A sequential molecular dynamics/quantum mechanics (MD/QM) procedure was used to investigate the effects of solute polarization and flexibility on the solvatochromism of a brominated merocyanine dye (MeBM) in water. Relevant structures for the solution were generated using MD simulations. The structural analysis indicates that the flexibility of MeBM is limited; showing small amplitudes both for dihedral isomerization and for the angle formed between the normal vectors of the pyridine and phenolate rings. The solvatochromic shift in the p-p* electronic transition was studied using both the PM6/CI and PM6/CI/COSMO methods in the gas phase as well as in the solution phase (solute þ first solvation shell). The results obtained with the use of the hybrid polarizable continuum model/discrete description are in good agreement with available experimental values and indicate that the polarization of the solute plays a more significant role in the solvatochromism of MeBM than its flexibility.

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Section: Quantum Mechanics: Vertical Electronic Transition Energies Asupporting

confidence: 86%

“…In the absence of explicit solvation by water molecules (highly dipolar solvent), both the polarization and the flexibility of the solute play minor roles in the average energy of electronic transition according to the results from the COSMO treatment. This effect was not expected for less polar solvents [39]. iii.…”

Section: Table IImentioning

confidence: 83%

Effect of solute flexibility and polarization on the solvatochromic shift of a brominated merocyanine dye in water: A sequential MD/QM study

Malaspina¹,

Fileti²,

Bastos³

2011

Int J of Quantum Chemistry

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“…Table 2 shows the relative error of the different long-range exchange functionals compared with experimental results at various separation parameters. The results showed that the error is dependent on the type of algorithm used to [39] or the implementation of an explicit solvation model [40][41][42] could provide a more realistic depiction of the dye in solvent condition that gives closer agreement with the experimental excitation energies. From our results, Q y -band undergoes HOMO ?…”

Section: Excitation Energiesmentioning

confidence: 63%

Molecular design of distorted push–pull porphyrins for dye-sensitized solar cells

2012

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A series of distorted push-pull meso-substituted porphyrin analogues with different acceptor groups and additional electron-donating substituents are investigated as organic sensitizers for application in dye-sensitized solar cells (DSSCs) using density functional theory (DFT) and time-dependent DFT approach. The donor was modified by interchanging methyl group with methoxy and extending the p-conjugation. The acceptor group was assessed based on cyanoacrylic (A analogues) or methylenemalonic (B analogues) acid groups. Benchmark calculations using YD1 as reference indicated that the best method to depict the excitation energies was with TDxB97X-D exchange-correlation (xc) functional while the computational protocol for computing redox potentials was found to be with the M06-2X xc functional based on vertical DSCF method. The absorption spectra of all the porphyrin analogues were red-shifted and produced higher oscillator strengths, especially at the Q-bands as compared to the reference molecule. Among the analogues, A2-OMe and B2-OMe are good candidates for sensitizers in DSSCs due to its larger hyperpolarizabilities, better light-harvesting efficiencies, proper matching of the ground-state oxidation potentials with respect to the I À =I À 3 redox couple, and higher dipole moment of the adsorbed analogues. This study further enhances the role of theoretical calculations in the molecular design of sensitizers for DSSCs in an effort to produce a highly efficient dye.

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“…Description of these models and variants can be found in recent reviews [28,29]. A comparison using applications in absorption spectrum in different solvents has recently been made [30].…”

Section: Introductionmentioning

confidence: 99%

Continuum, discrete, and explicit solvation models for describing the low‐lying absorption spectrum of the pterin acid in aqueous environment

Jaramillo

Coutinho

Canuto

2010

Int J of Quantum Chemistry

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ABSTRACT:The absorption spectrum of the acid form of pterin in water was investigated theoretically. Different procedures using continuum, discrete, and explicit models were used to include the solvation effect on the absorption spectrum, characterized by two bands. The discrete and explicit models used Monte Carlo simulation to generate the liquid structure and time-dependent density functional theory (B3LYP/6-31Gþ(d)) to obtain the excitation energies. The discrete model failed to give the correct qualitative effect on the second absorption band. The continuum model, in turn, has given a correct qualitative picture and a semiquantitative description. The explicit use of 29 solvent molecules, forming a hydration shell of 6 Å , embedded in the electrostatic field of the remaining solvent molecules, gives absorption transitions at 3.67 and 4.59 eV in excellent agreement with the S 0 -S 1 and S 0 -S 2 absorption bands at of 3.66 and 4.59 eV, respectively, that characterize the experimental spectrum of pterin in water environment.

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Solvent effects on the electronic absorption spectrum of camphor using continuum, discrete or explicit approaches

Cited by 25 publications

References 23 publications

Effect of solute flexibility and polarization on the solvatochromic shift of a brominated merocyanine dye in water: A sequential MD/QM study

Effect of solute flexibility and polarization on the solvatochromic shift of a brominated merocyanine dye in water: A sequential MD/QM study

Molecular design of distorted push–pull porphyrins for dye-sensitized solar cells

Continuum, discrete, and explicit solvation models for describing the low‐lying absorption spectrum of the pterin acid in aqueous environment

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