Binding of polyvinylpyrrolidone to Ag surfaces: Insight into a structure-directing agent from dispersion-corrected density functional theory

Wissam A. Saidi, Haijun Feng, Kristen Ann Fichthorn

Research output: Contribution to journalArticle

60 Citations (Scopus)

Abstract

We use dispersion-corrected density functional theory (DFT) to resolve the role of polyvinylpyrrolidone (PVP) in the shape-selective synthesis of Ag nanostructures by probing the interaction of its 2-pyrrolidone (2P) ring with Ag(100) and Ag(111). We employ two different semiempirical methods for including van der Waals (vdW) interactions in DFT calculations: DFT+vdWsurf and DFT-D2. We find that DFT-D2, in its original parametrization, overestimates the Ag metal dispersion interaction and causes an unphysical herringbone-like reconstruction of Ag(100). This can be remedied in DFT-D2 by using modified vdW parameters for Ag that account for many-body screening effects. The results obtained using DFT-D2 with the modified parameters agree well with experiment and with DFT+vdWsurf results. We find that 2P binds more strongly to Ag(100) than Ag(111), consistent with experiment. We analyze the origins of the surface-sensitive binding and find that vdW attraction is stronger on Ag(111), but the direct chemical bonding of 2P is stronger on Ag(100). We also study the influence of strain on binding energies and find that tension tends to lower the vdW interaction with the surfaces, while increasing the direct chemical-bonding interaction, consistent with the d-band center model. Overall, our work indicates that strain has little impact on the structure-directing capabilities of PVP, which is consistent with the fact that strained, 5-fold twinned Ag nanowires have extensive {100} facets and relative small {111} facets.

Original languageEnglish (US)
Pages (from-to)1163-1171
Number of pages9
JournalJournal of Physical Chemistry C
Volume117
Issue number2
DOIs
StatePublished - Jan 17 2013

Fingerprint

Povidone
Density functional theory
density functional theory
interactions
flat surfaces
Binding energy
Nanowires
attraction
Nanostructures
Screening
nanowires
screening
binding energy
Metals
Experiments
causes
rings
synthesis

All Science Journal Classification (ASJC) codes

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

Cite this

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title = "Binding of polyvinylpyrrolidone to Ag surfaces: Insight into a structure-directing agent from dispersion-corrected density functional theory",
abstract = "We use dispersion-corrected density functional theory (DFT) to resolve the role of polyvinylpyrrolidone (PVP) in the shape-selective synthesis of Ag nanostructures by probing the interaction of its 2-pyrrolidone (2P) ring with Ag(100) and Ag(111). We employ two different semiempirical methods for including van der Waals (vdW) interactions in DFT calculations: DFT+vdWsurf and DFT-D2. We find that DFT-D2, in its original parametrization, overestimates the Ag metal dispersion interaction and causes an unphysical herringbone-like reconstruction of Ag(100). This can be remedied in DFT-D2 by using modified vdW parameters for Ag that account for many-body screening effects. The results obtained using DFT-D2 with the modified parameters agree well with experiment and with DFT+vdWsurf results. We find that 2P binds more strongly to Ag(100) than Ag(111), consistent with experiment. We analyze the origins of the surface-sensitive binding and find that vdW attraction is stronger on Ag(111), but the direct chemical bonding of 2P is stronger on Ag(100). We also study the influence of strain on binding energies and find that tension tends to lower the vdW interaction with the surfaces, while increasing the direct chemical-bonding interaction, consistent with the d-band center model. Overall, our work indicates that strain has little impact on the structure-directing capabilities of PVP, which is consistent with the fact that strained, 5-fold twinned Ag nanowires have extensive {100} facets and relative small {111} facets.",
author = "Saidi, {Wissam A.} and Haijun Feng and Fichthorn, {Kristen Ann}",
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Binding of polyvinylpyrrolidone to Ag surfaces : Insight into a structure-directing agent from dispersion-corrected density functional theory. / Saidi, Wissam A.; Feng, Haijun; Fichthorn, Kristen Ann.

In: Journal of Physical Chemistry C, Vol. 117, No. 2, 17.01.2013, p. 1163-1171.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Binding of polyvinylpyrrolidone to Ag surfaces

T2 - Insight into a structure-directing agent from dispersion-corrected density functional theory

AU - Saidi, Wissam A.

AU - Feng, Haijun

AU - Fichthorn, Kristen Ann

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AB - We use dispersion-corrected density functional theory (DFT) to resolve the role of polyvinylpyrrolidone (PVP) in the shape-selective synthesis of Ag nanostructures by probing the interaction of its 2-pyrrolidone (2P) ring with Ag(100) and Ag(111). We employ two different semiempirical methods for including van der Waals (vdW) interactions in DFT calculations: DFT+vdWsurf and DFT-D2. We find that DFT-D2, in its original parametrization, overestimates the Ag metal dispersion interaction and causes an unphysical herringbone-like reconstruction of Ag(100). This can be remedied in DFT-D2 by using modified vdW parameters for Ag that account for many-body screening effects. The results obtained using DFT-D2 with the modified parameters agree well with experiment and with DFT+vdWsurf results. We find that 2P binds more strongly to Ag(100) than Ag(111), consistent with experiment. We analyze the origins of the surface-sensitive binding and find that vdW attraction is stronger on Ag(111), but the direct chemical bonding of 2P is stronger on Ag(100). We also study the influence of strain on binding energies and find that tension tends to lower the vdW interaction with the surfaces, while increasing the direct chemical-bonding interaction, consistent with the d-band center model. Overall, our work indicates that strain has little impact on the structure-directing capabilities of PVP, which is consistent with the fact that strained, 5-fold twinned Ag nanowires have extensive {100} facets and relative small {111} facets.

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