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Inorganics 2017, 5(3), 41;

Computing Free Energies of Hydroxylated Silica Nanoclusters: Forcefield versus Density Functional Calculations

Departament de Ciència de Materials i Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, E-08028 Barcelona, Spain
Dipartimento di Chimica and NIS Centre, Università degli Studi di Torino, Via P. Giuria 7, I-10125 Torino, Italy
Institució Catalana de Recerca i Estudis Avançats (ICREA), E-08010 Barcelona, Spain
Author to whom correspondence should be addressed.
Academic Editor: Duncan H. Gregory
Received: 18 May 2017 / Revised: 19 June 2017 / Accepted: 24 June 2017 / Published: 29 June 2017
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We assess the feasibility of efficiently calculating accurate thermodynamic properties of (SiO2)n·(H2O)m nanoclusters, using classical interatomic forcefields (FFs). Specifically, we use a recently parameterized FF for hydroxylated bulk silica systems (FFSiOH) to calculate zero-point energies and thermal contributions to vibrational internal energy and entropy, in order to estimate the free energy correction to the internal electronic energy of these nanoclusters. The performance of FFSiOH is then benchmarked against the results of corresponding calculations using density functional theory (DFT) calculations employing the B3LYP functional. Results are reported first for a set of (SiO2)n·(H2O)m clusters with n = 4, 8 and 16, each possessing three different degrees of hydroxylation (R = m/n): 0.0, 0.25 and 0.5. Secondly, we consider five distinct hydroxylated nanocluster isomers with the same (SiO2)16·(H2O)4 composition. Finally, the free energies for the progressive hydroxylation of three nanoclusters with R = 0–0.5 are also calculated. Our results demonstrate that, in all cases, the use of FFSiOH can provide estimates of thermodynamic properties with an accuracy close to that of DFT calculations, and at a fraction of the computational cost. View Full-Text
Keywords: hydroxylated silica; nanoclusters; free energy; density functional theory; forcefields hydroxylated silica; nanoclusters; free energy; density functional theory; forcefields

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Macià Escatllar, A.; Ugliengo, P.; Bromley, S.T. Computing Free Energies of Hydroxylated Silica Nanoclusters: Forcefield versus Density Functional Calculations. Inorganics 2017, 5, 41.

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