Investigation of the role of the C-PCM solvent effect in reactivity indices

Ordon, Piotr; Tachibana, Akitomo

doi:10.1007/bf02708365

Cited by 41 publications

(20 citation statements)

References 21 publications

(22 reference statements)

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“…Consequently, any change in the molecular or electronic structure within the solvent induces an internal force. 53 C-PCM is known to provide reliable results for organic compounds, for both neutral and charged solutes, with solute geometries optimized in vacuo, and its results are in close agreement with those of the PCM model. 45 Fig.…”

Section: Resultsmentioning

confidence: 62%

DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Balanay

Kim

2008

Phys. Chem. Chem. Phys.

137

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Density functional theory (DFT) and time-dependent DFT calculations have been employed to model Zn meso-tetraphenylporphyrin (ZnTPP) complexes having different b-substituents, in order to design an efficient sensitizer for dye-sensitized solar cells. To calculate the excited states of the porphyrin analogues, at least the TD-B3LYP/6-31G* level of theory is needed to replicate the experimental absorption spectra. Solvation results were found to be invariant with respect to the type of model used (PCM vs. C-PCM). Most of the electronic transitions based on Gouterman's four-orbital model of ZnTPP-A and ZnTPP-B are p -p* transitions, so that cell efficiency can be enhanced by increasing the p-conjugation and electron-withdrawing capability of the bsubstituent. This proposition was tested by inserting thiophene into the b-substituent of ZnTPP-A to form a new analogue, ZnTPP-C. Compared with ZnTPP-A and ZnTPP-B, ZnTPP-C has a smaller band gap, which brings LUMO closer to the conduction band of TiO 2 , and a red-shifted absorption spectrum with higher extinction coefficients, especially in the Q-band position.

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Section: Resultsmentioning

confidence: 62%

DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Balanay

Kim

2008

Phys. Chem. Chem. Phys.

137

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“…We have studied molecular reactivity modifications along the course of chemical reaction for a long time [1][2][3]. We have developed regional chemical potential evolution and identified the most reactive state along the IRC reaction path [4].…”

Section: Introductionmentioning

confidence: 99%

Evolution of the atomic valence observed by the reaction fragility spectra on the reaction path

2019

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The computational fragility spectra of atoms on the reaction path are presented for a selection of canonical processes represented by an amino group rotation around the (X)HC-NH(Y) bond (X = O, S; Y=H, CH 3). Calculated spectra are found to very accurately describe the variation of atomic valence. Significant linear correlation is also demonstrated between the Wiberg bond indices and the corresponding elements of the connectivity matrix, instrumental for calculation of the spectra. Demonstrated atomic fragility spectra contain rich and subtle information on the variation of the bonding status of all atoms, including the weak interacting individual hydrogens. Correlation with the atomic valences confirm the earlier finding that the spectra contain a picture of the electron density flow upon a reaction.

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“…The TD‐DFT was performed with 10 singlet excited states using CAM‐B3LYP functional and 6‐311+G(d) basis set except for iodine atom that used the LANL2DZ basis set. Conductor like polarizable continuum model (CPCM) was used with CH 2 Cl 2 parameters. Molecular orbitals were plotted with Jimp2 visualizing program .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, optical, and electrochemical properties, and theoretical calculations of BODIPY containing triphenylamine

Wanwong

Surawatanawong

Khumsubdee

et al. 2016

Heteroatom Chemistry

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The boron dipyrromethene (BODIPY) triads consisting of two triphenylamine units as electron donor (D) and BODIPY core as electron acceptor (A; B3, and B4) have been synthesized using facile palladium cross‐coupling reactions to broaden the absorption of the BODIPY dyes. All dyes and intermediates were characterized by 1H NMR, 11B NMR, 13C NMR, and 19F NMR spectroscopies, UV–Vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and time‐dependent density functional theory calculations. It was found that an increase in conjugation to the BODIPY core systematically extended the absorption and emission wavelength maxima. As a consequence, B4 containing the D–π–A–π–D structure, exhibited the longest absorption and emission maxima at 597 and 700 nm, respectively, with 1.8 eV in optical bandgap. The 96 nm red‐shifted absorption of B4 as compared to the unsubstituted BODIPY (B1) indicated the effective electronic communication between triphenylamine and BODIPY. This suggested that the proper alignment of triphenylamine and BODIPY triad could lead to broader absorption and suitable low energy bandgap. Furthermore, the molecular modeling has been employed to analyze the electronic and optical properties of the dyes. We found that the optical, electrochemical, and theoretical bandgaps of all dyes were in good agreement.

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Investigation of the role of the C-PCM solvent effect in reactivity indices

Cited by 41 publications

References 21 publications

DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Evolution of the atomic valence observed by the reaction fragility spectra on the reaction path

Synthesis, optical, and electrochemical properties, and theoretical calculations of BODIPY containing triphenylamine

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