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

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Marco Antonio Chaer Nascimento

Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 4))

Abstract

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.

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Author information

Authors and Affiliations

  1. Instituto de Física, Universidade de São Paulo, CP 66318, São Paulo, SP, 05315-970, Brazil

    Rodrigo M. Gester & Sylvio Canuto

  2. Faculdade de Ciências Exatas e Naturais, Universidade Federal do Pará, Marabá, PA, 68505-080, Brazil

    Rodrigo M. Gester

  3. Instituto de Física, Universidade Federal de Goiás, CP 131, Goiânia, GO, 74001-970, Brazil

    Herbert C. Georg & Tertius L. Fonseca

  4. Department of Physics, Northeastern University and I-MIT (CONICET), AV. Libertad 5500, W 3404 AAS, Corrientes, Argentina

    Patricio F. Provasi

Authors
  1. Rodrigo M. Gester
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  2. Herbert C. Georg
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  3. Tertius L. Fonseca
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  4. Patricio F. Provasi
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  5. Sylvio Canuto
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Corresponding authors

Correspondence to Rodrigo M. Gester or Sylvio Canuto .

Editor information

Editors and Affiliations

  1. Departamento de Química Fundamental, Instituto de Química, University of São Paulo, São Paulo, Brazil

    Fernando R. Ornellas

  2. REQUIMTE, Depart. de Química e Bioquimic, University of Porto, Faculty of Science, Porto, Portugal

    Maria João Ramos

Additional information

Dedicated to Professor Marco Antonio Chaer Nascimento and published as part of the special collection of articles celebrating his 65th birthday.

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Gester, R.M., Georg, H.C., Fonseca, T.L., Provasi, P.F., Canuto, S. (2014). A simple analysis of the influence of the solvent-induced electronic polarization on the 15N magnetic shielding of pyridine in water. In: Ornellas, F., João Ramos, M. (eds) Marco Antonio Chaer Nascimento. Highlights in Theoretical Chemistry, vol 4. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41163-2_11

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