Density Functional Tight-Binding Simulations Reveal the Presence of Surface Defects on the Quartz (101)–Water Interface

Yuan, Ke; Rampal, Nikhil; Fenter, Paul; Kubicki, James D.; Stack, Andrew G.; Irle, Stephan

doi:10.1021/acs.jpcc.1c03689

Density Functional Tight-Binding Simulations Reveal the Presence of Surface Defects on the Quartz (101)–Water Interface

Journal Article · Fri Jul 09 04:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c03689· OSTI ID:1814367

^[1]; Rampal, Nikhil ^[2]; ^[3]; ^[4]; ^[1]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Columbia Univ., New York, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Texas at El Paso, TX (United States)

Understanding the structure and reactivity of quartz–water interfaces is critical for numerous applications in the geological, environmental, and biological sciences. However, disagreements on the atomic-level structure of the interfaces between experiments and simulations are hampering our ability to predict the surface reactivity. Here, we used density functional tight-binding (DFTB)-based molecular dynamics to simulate a series of quartz (101) surfaces having different types and densities of surface defects in water and compared them with the structures determined by X-ray reflectivity measurements. The DFTB simulations are able to reproduce previous classical and quantum mechanical predictions of the pristine quartz (101)–water interface that disagree with experimental observations. To remedy this situation, a set of defective quartz surfaces having various surface silicon (Si) vacancies were built as indicated by recent experimental studies. We found that the rotation of surface [SiO₄] tetrahedra near Si vacancies can lead to outward displacements of Si atoms similar to those observed in the experiments. The presence of additional surface Si vacancies caused inward relaxations of terminal oxygens through the formation of hydrogen bonds. Finally, the overall results indicate that the quartz (101)–water interface may include a mixture of geminal (≡Si–(OH)₂)- and vicinal (≡Si–OH)-type silanol groups together with the presence of surface Si vacancies.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1814367

Alternate ID(s):: OSTI ID: 1839999

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 29 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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