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Tetraethylorthosilicate as molecular precursor to the formation of amorphous silica networks. A DFT-SCRF study of the base catalyzed hydrolysis

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Abstract

Quantum chemical calculations using density functional theory have been carried out to investigate two chemical pathways for the last step of the hydrolysis of tetraethylorthosilicate (TEOS) in basic catalyzed environment. The two models that are introduced in this study depend on the number of water molecules involved at the base catalyzed hydrolysis. Solution equilibrium geometries of the molecules involved in the transition states, reactants and product complexes of the two chemical pathways were fully optimized at B3LYP level of theory with the standard 6-31+G(d) basis set, modeling solvent effects using a polarizable continuum solvation model (PCM). Both models predict relative low activation energies. However, the model with two water molecules seems to be more adequate to describe the basic hydrolysis. A natural bond orbital (NBO) analysis seems to show that the proton transfer from water to ethoxy group would occur through a large hyperconjugative interaction, LPO→σ*(O-H), which is related to the nonbonding oxygen lone pair orbital from ethoxy group with the vicinal σ*(O-H) anti bonding orbital O-H of a water molecule.

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Scheme 1
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Notes

  1. The SCRF methodology reveals one negative frequency for the energy minimum in the RC1, PC1, RC3 and PC3 complexes. All of them are low, corresponding to the movement of OH bond in H2O molecule or the rotation of CH3 group. In this way, a second low negative frequency appears in the TS3 calculation. No negative frequencies have been obtained from the calculations in gas phase what could confirm these ones as theoretical artifacts from the SCRF methodology.

  2. The conversion of solvation free energies at 298K to a standard state 1M is performed by adding +1.89kcalmol−1 to the computed solvation free energy.

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Acknowledgments

This research was supported by the Generalitat Valenciana (GV2008-122). Lorenzo Fernandez was supported by the Ramon y Cajal program by the Ministry of Science and Technology from Spain.

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Authors and Affiliations

  1. Institut de Ciència dels Materials de la Universitat de Valencia (ICMUV), P.O. Box 22085, E-46071, Valencia, Spain

    Lorenzo Fernandez, Julio Latorre, Carmen Guillem, Aurelio Beltrán & Pedro Amorós

  2. Department of Quim Fis, Universitat de Valencia, E-46100, Burjassot, Spain

    Iñaki Tuñón

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  1. Lorenzo Fernandez
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Fernandez, L., Tuñón, I., Latorre, J. et al. Tetraethylorthosilicate as molecular precursor to the formation of amorphous silica networks. A DFT-SCRF study of the base catalyzed hydrolysis. J Mol Model 18, 3301–3310 (2012). https://doi.org/10.1007/s00894-011-1345-4

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