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Comparison of polarizable continuum model and quantum mechanics/molecular mechanics solute electronic polarization: Study of the optical and magnetic properties of diazines in water
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10.1063/1.3644894
/content/aip/journal/jcp/135/14/10.1063/1.3644894
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/14/10.1063/1.3644894

Figures

Image of FIG. 1.
FIG. 1.

The structure of pyridazine and pyrazine molecules and the atomic labels.

Image of FIG. 2.
FIG. 2.

Calculated average values of the dipole moments of in-water pyridazine with respect to the number of iterations (filled square). Each point is obtained from an average involving 100 configurations. Also shown are the corresponding values using PCM (filled circle) and in values obtained after one MC simulation with the PCM polarization (open circle).

Image of FIG. 3.
FIG. 3.

Calculated mean charges in atoms (a) N(1,2), (b) C(1,2,3,4), and (c) H(1,2,3,4) of pyrazine, and (d) N(1,2), (e) C(1,2), C(3,4), (f) H(1,4), and H(2,3) of pyridazine with respect to the number of iterations. Each set of charges in each iteration as obtained from an average involving 100 statistically uncorrelated configurations. The PCM charges are shown in the filled dark (red) circles and the open circles are the values obtained after one MC simulation with the PCM polarization. The dotted lines represent the converged values presented in Table I.

Image of FIG. 4.
FIG. 4.

Radial distribution functions between the (a) center of mass and the (b) nitrogen atom of solute and the oxygen or hydrogen atom of water molecules of the solvent for pyridazine. (c) The histogram of the pairwise energy interaction between pyridazine and the solvent water molecules in both polarization schemes.

Image of FIG. 5.
FIG. 5.

Dependence of the experimental 15N chemical shift of (a) pyridazine and (b) pyrazine with the Reichardt normalized polarity69 for 12 different solvents. Numerical values from the experiments of Witanowski et al. 68 with different solvents: 1 = cyclohexane, 2 = CCl4, 3 = Et2O, 4 = benzene, 5 = dioxane, 6 = acetone, 7 = DMSO, 8 = CH2C12, 9 = CHCl3, 10 = EtOH, 11 = MeOH, and 12 = H2O.

Tables

Generic image for table
Table I.

Atomic charges (e) of pyridazine and pyrazine obtained by PCM and iterative polarizations. The dipole moments for each type of polarization are also shown.

Generic image for table
Table II.

Statistics (in percentage) of solute-solvent hydrogen-bonding water molecules of pyridazine and pyrazine in water for both polarization schemes.

Generic image for table
Table III.

Experimental results for the lowest n → π* absorption transition (in cm−1) of pyridazine and pyrazine in low polarity solvents and water.

Generic image for table
Table IV.

Calculated values for the lowest n → π* absorption transition (in cm−1) of pyridazine and pyrazine using 100 statistically uncorrelated configurations obtained from the MC simulations. The absorption energies are calculated using TD DFT B3LYP/6-311+G(d) level and the error bars are the statistical error for the average values. Results in parenthesis were obtained using a geometry optimized with PCM.

Generic image for table
Table V.

Theoretical values for the lowest n → π* absorption transition (in cm−1) of pyridazine and pyrazine in water and the respective shifts with respect to the gas phase values.

Generic image for table
Table VI.

Theoretical values for the 15N isotropic magnetic shielding and gas-water shift (in ppm) of pyridazine and pyrazine using 100 statistically uncorrelated configurations obtained by the MC simulations using the two polarization schemes. The magnetic shieldings are calculated using DFT/B3LYP/GIAO/aug-pcS2(N)/pcS2(C,O,H) level and the error bars are the statistical error for the average values. Results in parenthesis were obtained using a geometry optimized with PCM.

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/content/aip/journal/jcp/135/14/10.1063/1.3644894
2011-10-10
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Comparison of polarizable continuum model and quantum mechanics/molecular mechanics solute electronic polarization: Study of the optical and magnetic properties of diazines in water
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/14/10.1063/1.3644894
10.1063/1.3644894
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