Degenerate Four-Wave Mixing in Solution by Cubic Response Theory and the Polarizable Continuum Model

This research examined the effects of solvent polarity and temperature on the tautomerization of a carbonitrile molecule at CAM-B3LYP/6-311G (d,p) level of theory. The selected solvents were n-hexane, diethyl ether, pyridine, ethanol, methanol, and water. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects were explored on the energy barrier, frontier orbitals energies, and HOMO-LUMO gap. Dependencies of thermodynamic parameters (ΔG and ΔH) on the dielectric constants of solvents were also tested. Specifically, the temperature dependencies of the thermodynamics parameters were studied within 100–1000 K range. The rate constant of the tautomerism reaction was computed from 300 to 1200 K, in the gas phase.

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Degenerate four wave mixing study of conformational transition of a polydiacetylene, poly‐4‐BCMU, in solution

The Journal of Chemical Physics ◽

10.1063/1.451301 ◽

1986 ◽

Vol 85 (2) ◽

pp. 1077-1080 ◽

Cited By ~ 4

Author(s):

Peijun Cong ◽

Yang Pang ◽

Paras N. Prasad

Keyword(s):

Conformational Transition ◽

Four Wave Mixing ◽

Wave Mixing ◽

Degenerate Four Wave Mixing

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THEORETICAL CALCULATION OF pKb VALUES FOR ANILINES AND SULFONAMIDE DRUGS IN AQUEOUS SOLUTION

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633612500307 ◽

2012 ◽

Vol 11 (02) ◽

pp. 283-295 ◽

Cited By ~ 19

Author(s):

BAHRAM GHALAMI-CHOOBAR ◽

ALI GHIAMI-SHOMAMI ◽

PARIA NIKPARSA

Keyword(s):

Gas Phase ◽

Continuum Model ◽

Correlation Equation ◽

Polarizable Continuum Model ◽

Free Energies ◽

Pcm Model ◽

Solvation Models ◽

Polarizable Continuum ◽

Better Than ◽

Good Agreement

In this work, calculations of p K b values have been performed for aniline and its substituted derivatives and sulfonamide drugs by using Gaussian 98 software package. Gas-phase energies were calculated with HF /6-31 G ** and B3LYP /6-31 G ** levels of theory. Free energies of solvation have been computed using the polarizable continuum model (PCM), conductor-like polarizable continuum model (CPCM) and the integral equation formalism-polarizable continuum model (IEFPCM) at the same levels which have been used for geometry determination in the gas-phase. The results show that the calculated p K b values using the B3LYP /6-31 G ** are better than those using the corresponding HF /6-31 G **. At first, the correlation equation was found to determine the p K b values of the investigated anilines. Then, this correlation equation was used to calculate the p K b values of the sulfonamide drugs. The results obtained indicate that the PCM model is a suitable solvation model for calculating p K b values in comparison to the other solvation models. For the investigated compounds a good agreement between the experimental and the calculated p K b values was also observed.

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