Binding of small molecules to a silica surface: Comparing experimental and theoretical results

Decarlos E. Taylor, Keith A Runge, Marshall G. Cory, Douglas S. Burns, Joseph L. Vasey, John D. Hearn, Michael V. Henley

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

A multiscale method for systematically generating predictive models for probe-surface interactions and its independent experimental verification is described. The interaction of three probe molecules (H 2O, NH 3, and NO) with silica was studied using experiment, theoretical quantum chemistry, and molecular dynamics calculations. Quantum chemical (QC) methods were used to compute binding enthalpies and vibrational (infrared, IR) spectra of molecule-surface pairs for three unique surface silanol sites. The probe-surface IR spectral shifts induced by the interaction of the probe molecules with the surface silanol sites were also computed and compared to experiment. The computed IR results are comparable to those of experiment and (a) verified that the surface that has been created using simulation is indeed similar to the experimental surface and (b) shed insight into the underlying physical process leading to the observed shifts. The theoretically determined enthalpies of adsorption (ΔH ads) compared well with experiment falling within the uncertainty of those measured using inverse gas chromatography. For water, ΔH ads,350K= - 13.5kcal/mol (calculated) versus -13.6 ± 2.8kcal/mol (experimental, 330 K < T expt < 370 K). For ammonia, ΔH ads,353K = -15.2 kcal/mol (calculated) versus -12.7 ± 2.9 kcal/mol (experimental, 323 K < T expt < 383 K). Finally, for nitric oxide, ΔH ads,253K = -4.23 kcal/mol (calculated) versus -4.03 ± 0.35 kcal/mol (experimental, 243 K < T expt < 263 K).

Original languageEnglish (US)
Pages (from-to)24734-24742
Number of pages9
JournalJournal of Physical Chemistry C
Volume115
Issue number50
DOIs
StatePublished - Dec 22 2011
Externally publishedYes

Fingerprint

Silicon Dioxide
Silica
silicon dioxide
Molecules
molecules
probes
Infrared radiation
enthalpy
Enthalpy
Experiments
sheds
shift
Quantum chemistry
quantum chemistry
nitric oxide
gas chromatography
falling
Nitric oxide
vibrational spectra
surface reactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Taylor, D. E., Runge, K. A., Cory, M. G., Burns, D. S., Vasey, J. L., Hearn, J. D., & Henley, M. V. (2011). Binding of small molecules to a silica surface: Comparing experimental and theoretical results. Journal of Physical Chemistry C, 115(50), 24734-24742. https://doi.org/10.1021/jp205479v

Binding of small molecules to a silica surface : Comparing experimental and theoretical results. / Taylor, Decarlos E.; Runge, Keith A; Cory, Marshall G.; Burns, Douglas S.; Vasey, Joseph L.; Hearn, John D.; Henley, Michael V.

In: Journal of Physical Chemistry C, Vol. 115, No. 50, 22.12.2011, p. 24734-24742.

Research output: Contribution to journalArticle

Taylor, DE, Runge, KA, Cory, MG, Burns, DS, Vasey, JL, Hearn, JD & Henley, MV 2011, 'Binding of small molecules to a silica surface: Comparing experimental and theoretical results', Journal of Physical Chemistry C, vol. 115, no. 50, pp. 24734-24742. https://doi.org/10.1021/jp205479v
Taylor, Decarlos E. ; Runge, Keith A ; Cory, Marshall G. ; Burns, Douglas S. ; Vasey, Joseph L. ; Hearn, John D. ; Henley, Michael V. / Binding of small molecules to a silica surface : Comparing experimental and theoretical results. In: Journal of Physical Chemistry C. 2011 ; Vol. 115, No. 50. pp. 24734-24742.
@article{c9cea0032d884b57bc1eda913e7b6f89,
title = "Binding of small molecules to a silica surface: Comparing experimental and theoretical results",
abstract = "A multiscale method for systematically generating predictive models for probe-surface interactions and its independent experimental verification is described. The interaction of three probe molecules (H 2O, NH 3, and NO) with silica was studied using experiment, theoretical quantum chemistry, and molecular dynamics calculations. Quantum chemical (QC) methods were used to compute binding enthalpies and vibrational (infrared, IR) spectra of molecule-surface pairs for three unique surface silanol sites. The probe-surface IR spectral shifts induced by the interaction of the probe molecules with the surface silanol sites were also computed and compared to experiment. The computed IR results are comparable to those of experiment and (a) verified that the surface that has been created using simulation is indeed similar to the experimental surface and (b) shed insight into the underlying physical process leading to the observed shifts. The theoretically determined enthalpies of adsorption (ΔH ads) compared well with experiment falling within the uncertainty of those measured using inverse gas chromatography. For water, ΔH ads,350K= - 13.5kcal/mol (calculated) versus -13.6 ± 2.8kcal/mol (experimental, 330 K < T expt < 370 K). For ammonia, ΔH ads,353K = -15.2 kcal/mol (calculated) versus -12.7 ± 2.9 kcal/mol (experimental, 323 K < T expt < 383 K). Finally, for nitric oxide, ΔH ads,253K = -4.23 kcal/mol (calculated) versus -4.03 ± 0.35 kcal/mol (experimental, 243 K < T expt < 263 K).",
author = "Taylor, {Decarlos E.} and Runge, {Keith A} and Cory, {Marshall G.} and Burns, {Douglas S.} and Vasey, {Joseph L.} and Hearn, {John D.} and Henley, {Michael V.}",
year = "2011",
month = "12",
day = "22",
doi = "10.1021/jp205479v",
language = "English (US)",
volume = "115",
pages = "24734--24742",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "50",

}

TY - JOUR

T1 - Binding of small molecules to a silica surface

T2 - Comparing experimental and theoretical results

AU - Taylor, Decarlos E.

AU - Runge, Keith A

AU - Cory, Marshall G.

AU - Burns, Douglas S.

AU - Vasey, Joseph L.

AU - Hearn, John D.

AU - Henley, Michael V.

PY - 2011/12/22

Y1 - 2011/12/22

N2 - A multiscale method for systematically generating predictive models for probe-surface interactions and its independent experimental verification is described. The interaction of three probe molecules (H 2O, NH 3, and NO) with silica was studied using experiment, theoretical quantum chemistry, and molecular dynamics calculations. Quantum chemical (QC) methods were used to compute binding enthalpies and vibrational (infrared, IR) spectra of molecule-surface pairs for three unique surface silanol sites. The probe-surface IR spectral shifts induced by the interaction of the probe molecules with the surface silanol sites were also computed and compared to experiment. The computed IR results are comparable to those of experiment and (a) verified that the surface that has been created using simulation is indeed similar to the experimental surface and (b) shed insight into the underlying physical process leading to the observed shifts. The theoretically determined enthalpies of adsorption (ΔH ads) compared well with experiment falling within the uncertainty of those measured using inverse gas chromatography. For water, ΔH ads,350K= - 13.5kcal/mol (calculated) versus -13.6 ± 2.8kcal/mol (experimental, 330 K < T expt < 370 K). For ammonia, ΔH ads,353K = -15.2 kcal/mol (calculated) versus -12.7 ± 2.9 kcal/mol (experimental, 323 K < T expt < 383 K). Finally, for nitric oxide, ΔH ads,253K = -4.23 kcal/mol (calculated) versus -4.03 ± 0.35 kcal/mol (experimental, 243 K < T expt < 263 K).

AB - A multiscale method for systematically generating predictive models for probe-surface interactions and its independent experimental verification is described. The interaction of three probe molecules (H 2O, NH 3, and NO) with silica was studied using experiment, theoretical quantum chemistry, and molecular dynamics calculations. Quantum chemical (QC) methods were used to compute binding enthalpies and vibrational (infrared, IR) spectra of molecule-surface pairs for three unique surface silanol sites. The probe-surface IR spectral shifts induced by the interaction of the probe molecules with the surface silanol sites were also computed and compared to experiment. The computed IR results are comparable to those of experiment and (a) verified that the surface that has been created using simulation is indeed similar to the experimental surface and (b) shed insight into the underlying physical process leading to the observed shifts. The theoretically determined enthalpies of adsorption (ΔH ads) compared well with experiment falling within the uncertainty of those measured using inverse gas chromatography. For water, ΔH ads,350K= - 13.5kcal/mol (calculated) versus -13.6 ± 2.8kcal/mol (experimental, 330 K < T expt < 370 K). For ammonia, ΔH ads,353K = -15.2 kcal/mol (calculated) versus -12.7 ± 2.9 kcal/mol (experimental, 323 K < T expt < 383 K). Finally, for nitric oxide, ΔH ads,253K = -4.23 kcal/mol (calculated) versus -4.03 ± 0.35 kcal/mol (experimental, 243 K < T expt < 263 K).

UR - http://www.scopus.com/inward/record.url?scp=84857259247&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84857259247&partnerID=8YFLogxK

U2 - 10.1021/jp205479v

DO - 10.1021/jp205479v

M3 - Article

AN - SCOPUS:84857259247

VL - 115

SP - 24734

EP - 24742

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 50

ER -