A simple analysis of the influence of the solvent-induced electronic polarization on the 15N magnetic shielding of pyridine in water.

R. M. GESTER; H. C. GEORG; T. L. FONSECA ; P. F. PROVASI ; S. CANUTO

THEORETICAL CHEMISTRY ACCOUNTS

SPRINGER

Lugar: Berlin; Año: 2012 vol. 131 p. 1220 - 1228

1432-881X

Electronic polarization induced by the interaction of a reference molecule with a liquid environment is expected to affect the magnetic shielding constants.Understanding this effect using realistic theoretical models is important for proper use of nuclear magnetic resonance in molecular characterization. In this work, we consider the pyridine molecule in water as a model system to briefly investigate this aspect. Thus, Monte Carlo simulations and quantum mechanics calculations based on the B3LYP/6-311++G(d,p) are used to analyze different aspects of the solvent effects on the 15N magnetic shielding constant of pyridine in water. This includes in special the geometry relaxation and the electronic polarization of the solute by the solvent. The polarization effect is found to be very important, but, as expected for pyridine, the geometry relaxation contribution is essentially negligible. Using an average electrostatic model of the solvent, the magnetic shielding constant is calculated as -58.7 ppm, in good agreement with the experimental value of -56.3 ppm. The explicit inclusion of hydrogen-bonded water molecules embedded in the electrostatic field of the remaining solvent molecules gives the value of -61.8 ppm.