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Computational study of interactions and nuclear magnetic shielding constants in linear chains of formamide clusters

Journal of Molecular Modeling volume 20, Article number: 2320 (2014) Cite this article

Abstract

We investigated the energetic, structural, dielectric, and nuclear magnetic shielding properties of linear n-formamide clusters, with n up to 6, to quantitatively characterize cooperative effects in model biological systems. The geometries of the complexes were optimized at the MP2 and DFT/B3LYP levels by using the pc-2 and pc-3 basis sets, while the nuclear magnetic shielding constants were calculated by employing pcS-n type basis sets, which have been optimized specifically for density functional calculations of these properties. The interaction energies show the cooperative effect, which favors the successive addition of monomers. In addition, by analyzing structural changes in the intermolecular C=O, C–N and hydrogen O⋯H bonds, as well as in the average dipole moments as cluster size increases, we found that the cooperative interaction far exceeds that expected for electrostatic interactions. Such non-pairwise-additive effects are also reflected in the changes of the nuclear magnetic shielding constants. In particular, the negativity of O shielding decreases around 23 % from the monomer to the 6-formamide chain. It is possible to note the decrease in the shielding of H and in the deshielding of O as a result of their hydrogen bonding. However, the results obtained show that these variations in the extremes of formamide chains tend to zero, and the respective shielding values tend to stabilize as the number of monomers increases in the chain. Also, the cooperative effect increases in the middle of the chains, by decreasing the shielding for all atoms except that of O, which decreases its deshielding. These results could serve to guide improvements in current conventional models for simulating hydrogen bonded systems.

Total energy (solid circles) and interaction energy per hydrogen bond (open squares) for different n-formamide clusters. Blue dashed line Extrapolated values

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Acknowledgments

This work was supported by the MICINN grants FIS2010-18132, FIS2011-29596-C02-01, and COST Actions CM1002 (CODECS). The authors thank the Centro de Calculo (IFF-CSIC), SGAI (CSIC), and Centro de Supercomputación de Galicia (CESGA) for allocation of computer time.

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  1. Instituto de Física Fundamental, IFF-CSIC, Serrano 123, 28006, Madrid, Spain

    Marina Sánchez, Rita Prosmiti & Gerardo Delgado-Barrio

Authors
  1. Marina Sánchez
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  2. Rita Prosmiti
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  3. Gerardo Delgado-Barrio
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Correspondence to Rita Prosmiti.

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This paper belongs to Topical Collection QUITEL 2013

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Sánchez, M., Prosmiti, R. & Delgado-Barrio, G. Computational study of interactions and nuclear magnetic shielding constants in linear chains of formamide clusters. J Mol Model 20, 2320 (2014). https://doi.org/10.1007/s00894-014-2320-7

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  • DOI: https://doi.org/10.1007/s00894-014-2320-7

Keywords

  • Hydrogen bonding
  • Electronic structure calculations
  • Potential interactions