Surface binding of organophosphates on silica

Comparing experiment and theory

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

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A consistent embedding hierarchy is applied to the calculation of binding enthalpies for organophosphate molecules to a silica surface and compared to experiment. The interaction of four probe molecules, dimethyl methylphosphonate (DMMP), diisopropyl methylphosphonate (DIMP), diisopropyl fluorophosphate (DFP), and sarin, with the silica surface is examined. Quantum chemical methods are employed to compute binding enthalpies and vibrational spectra for all interactions between probe molecules and silanol sites on the silica surface. Comparison with experimentally measured infrared shifts indicates that the theoretically modeled adsorption sites are similar to those found in experiment. The calculated binding enthalpies agree well with experiment for sarin, ΔHads,443K = -22.0 kcal/mol (calculated) vs -18.8 ± 5.5 kcal/mol (measured, 433 K < Texpt < 453 K), and DIMP, ΔHads,463K = -26.9 kcal/mol (calculated) vs -29.3 ± 0.9 kcal/mol (measured, 453 K < Texpt < 473 K). Agreement with experiment is less good for DMMP, ΔHads,463K = -19.7 kcal/mol (calculated) vs -26.1 ± 1.5 kcal/mol (measured, 453 K < T expt < 473 K), and DFP, ΔHads,423K = -20.4 kcal/mol (calculated) vs -27.5 ± 3.1 kcal/mol (measured, 413 K < Texpt < 433 K).

Original languageEnglish (US)
Pages (from-to)2699-2708
Number of pages10
JournalJournal of Physical Chemistry C
Volume117
Issue number6
DOIs
StatePublished - Feb 14 2013
Externally publishedYes

Fingerprint

Organophosphates
fluorophosphate
Silicon Dioxide
enthalpy
Silica
Sarin
silicon dioxide
Enthalpy
Molecules
molecules
probes
Experiments
embedding
vibrational spectra
hierarchies
Vibrational spectra
interactions
adsorption
shift
Infrared radiation

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. (2013). Surface binding of organophosphates on silica: Comparing experiment and theory. Journal of Physical Chemistry C, 117(6), 2699-2708. https://doi.org/10.1021/jp306713d

Surface binding of organophosphates on silica : Comparing experiment and theory. / Taylor, Decarlos E.; Runge, Keith A; Cory, Marshall G.; Burns, Douglas S.; Vasey, Joseph L.; Hearn, John D.; Griffith, Kara; Henley, Michael V.

In: Journal of Physical Chemistry C, Vol. 117, No. 6, 14.02.2013, p. 2699-2708.

Research output: Contribution to journalArticle

Taylor, DE, Runge, KA, Cory, MG, Burns, DS, Vasey, JL, Hearn, JD, Griffith, K & Henley, MV 2013, 'Surface binding of organophosphates on silica: Comparing experiment and theory', Journal of Physical Chemistry C, vol. 117, no. 6, pp. 2699-2708. https://doi.org/10.1021/jp306713d
Taylor, Decarlos E. ; Runge, Keith A ; Cory, Marshall G. ; Burns, Douglas S. ; Vasey, Joseph L. ; Hearn, John D. ; Griffith, Kara ; Henley, Michael V. / Surface binding of organophosphates on silica : Comparing experiment and theory. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 6. pp. 2699-2708.
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