Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies

L. G. Hector, S. M. Opalka, G. A. Nitowski, L. Wieserman, D. J. Siegel, H. Yu, James Adams

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

The eleven ion vinyl phosphonic acid (VPA) molecule consists of a phosphorus ion that serves as a cationic anchor for two electron-rich functional groups, viz., a tripodal oxygen-rich base and vinyl hydrocarbon tail. Recent inelastic tunneling experiments have implied that VPA binds in a tridentate coordination though its base leaving the vinyl tail free to react with a resin in adhesive bonding applications. Using first-principles total energy calculations, the reaction enthalpies for bonding of a single VPA molecule to selected threefold sites on hydroxylated α-Al2O3(0001) are investigated. Tridentate, bidentate and unidentate coordinations, both with and without liberated water molecules, are examined to determine if the tridentate coordination is favored over the others and the extent to which the VPA molecule is sensitive to surface site geometry. The electron localization function is used to examine the extent of covalent character between the P-O bonds that anchor the VPA fragment to the oxide surface. Some comments on the entropic contributions of the VPA and H2O molecules to the binding energetics are offered, along with a discussion of the effects of H2O placement on the oxide surface and aluminum alloying agents.

Original languageEnglish (US)
Pages (from-to)1-20
Number of pages20
JournalSurface Science
Volume494
Issue number1
DOIs
StatePublished - Nov 10 2001

Fingerprint

Enthalpy
enthalpy
acids
Acids
Molecules
molecules
Anchors
Oxides
Ions
adhesive bonding
oxides
Electrons
Hydrocarbons
Aluminum
Alloying
Phosphorus
resins
Functional groups
alloying
phosphorus

Keywords

  • Aluminum oxide
  • Surface chemical reaction
  • Tunneling

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces

Cite this

Hector, L. G., Opalka, S. M., Nitowski, G. A., Wieserman, L., Siegel, D. J., Yu, H., & Adams, J. (2001). Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies. Surface Science, 494(1), 1-20. https://doi.org/10.1016/S0039-6028(01)01387-5

Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies. / Hector, L. G.; Opalka, S. M.; Nitowski, G. A.; Wieserman, L.; Siegel, D. J.; Yu, H.; Adams, James.

In: Surface Science, Vol. 494, No. 1, 10.11.2001, p. 1-20.

Research output: Contribution to journalArticle

Hector, LG, Opalka, SM, Nitowski, GA, Wieserman, L, Siegel, DJ, Yu, H & Adams, J 2001, 'Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies', Surface Science, vol. 494, no. 1, pp. 1-20. https://doi.org/10.1016/S0039-6028(01)01387-5
Hector LG, Opalka SM, Nitowski GA, Wieserman L, Siegel DJ, Yu H et al. Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies. Surface Science. 2001 Nov 10;494(1):1-20. https://doi.org/10.1016/S0039-6028(01)01387-5
Hector, L. G. ; Opalka, S. M. ; Nitowski, G. A. ; Wieserman, L. ; Siegel, D. J. ; Yu, H. ; Adams, James. / Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies. In: Surface Science. 2001 ; Vol. 494, No. 1. pp. 1-20.
@article{a80f58312e5e432bbd9dddb8cd9b92af,
title = "Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies",
abstract = "The eleven ion vinyl phosphonic acid (VPA) molecule consists of a phosphorus ion that serves as a cationic anchor for two electron-rich functional groups, viz., a tripodal oxygen-rich base and vinyl hydrocarbon tail. Recent inelastic tunneling experiments have implied that VPA binds in a tridentate coordination though its base leaving the vinyl tail free to react with a resin in adhesive bonding applications. Using first-principles total energy calculations, the reaction enthalpies for bonding of a single VPA molecule to selected threefold sites on hydroxylated α-Al2O3(0001) are investigated. Tridentate, bidentate and unidentate coordinations, both with and without liberated water molecules, are examined to determine if the tridentate coordination is favored over the others and the extent to which the VPA molecule is sensitive to surface site geometry. The electron localization function is used to examine the extent of covalent character between the P-O bonds that anchor the VPA fragment to the oxide surface. Some comments on the entropic contributions of the VPA and H2O molecules to the binding energetics are offered, along with a discussion of the effects of H2O placement on the oxide surface and aluminum alloying agents.",
keywords = "Aluminum oxide, Surface chemical reaction, Tunneling",
author = "Hector, {L. G.} and Opalka, {S. M.} and Nitowski, {G. A.} and L. Wieserman and Siegel, {D. J.} and H. Yu and James Adams",
year = "2001",
month = "11",
day = "10",
doi = "10.1016/S0039-6028(01)01387-5",
language = "English (US)",
volume = "494",
pages = "1--20",
journal = "Surface Science",
issn = "0039-6028",
publisher = "Elsevier",
number = "1",

}

TY - JOUR

T1 - Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3(0001) reaction enthalpies

AU - Hector, L. G.

AU - Opalka, S. M.

AU - Nitowski, G. A.

AU - Wieserman, L.

AU - Siegel, D. J.

AU - Yu, H.

AU - Adams, James

PY - 2001/11/10

Y1 - 2001/11/10

N2 - The eleven ion vinyl phosphonic acid (VPA) molecule consists of a phosphorus ion that serves as a cationic anchor for two electron-rich functional groups, viz., a tripodal oxygen-rich base and vinyl hydrocarbon tail. Recent inelastic tunneling experiments have implied that VPA binds in a tridentate coordination though its base leaving the vinyl tail free to react with a resin in adhesive bonding applications. Using first-principles total energy calculations, the reaction enthalpies for bonding of a single VPA molecule to selected threefold sites on hydroxylated α-Al2O3(0001) are investigated. Tridentate, bidentate and unidentate coordinations, both with and without liberated water molecules, are examined to determine if the tridentate coordination is favored over the others and the extent to which the VPA molecule is sensitive to surface site geometry. The electron localization function is used to examine the extent of covalent character between the P-O bonds that anchor the VPA fragment to the oxide surface. Some comments on the entropic contributions of the VPA and H2O molecules to the binding energetics are offered, along with a discussion of the effects of H2O placement on the oxide surface and aluminum alloying agents.

AB - The eleven ion vinyl phosphonic acid (VPA) molecule consists of a phosphorus ion that serves as a cationic anchor for two electron-rich functional groups, viz., a tripodal oxygen-rich base and vinyl hydrocarbon tail. Recent inelastic tunneling experiments have implied that VPA binds in a tridentate coordination though its base leaving the vinyl tail free to react with a resin in adhesive bonding applications. Using first-principles total energy calculations, the reaction enthalpies for bonding of a single VPA molecule to selected threefold sites on hydroxylated α-Al2O3(0001) are investigated. Tridentate, bidentate and unidentate coordinations, both with and without liberated water molecules, are examined to determine if the tridentate coordination is favored over the others and the extent to which the VPA molecule is sensitive to surface site geometry. The electron localization function is used to examine the extent of covalent character between the P-O bonds that anchor the VPA fragment to the oxide surface. Some comments on the entropic contributions of the VPA and H2O molecules to the binding energetics are offered, along with a discussion of the effects of H2O placement on the oxide surface and aluminum alloying agents.

KW - Aluminum oxide

KW - Surface chemical reaction

KW - Tunneling

UR - http://www.scopus.com/inward/record.url?scp=0035841374&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035841374&partnerID=8YFLogxK

U2 - 10.1016/S0039-6028(01)01387-5

DO - 10.1016/S0039-6028(01)01387-5

M3 - Article

AN - SCOPUS:0035841374

VL - 494

SP - 1

EP - 20

JO - Surface Science

JF - Surface Science

SN - 0039-6028

IS - 1

ER -