Abstract
We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the (√3 × √3) R30° pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 32753-32761 |
| Number of pages | 9 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 18 |
| Issue number | 48 |
| DOIs | |
| State | Published - Jan 1 2016 |
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All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Self-assembled monolayer structures of hexadecylamine on Cu surfaces : Density-functional theory. / Liu, Shih Hsien; Balankura, Tonnam; Fichthorn, Kristen Ann.
In: Physical Chemistry Chemical Physics, Vol. 18, No. 48, 01.01.2016, p. 32753-32761.Research output: Contribution to journal › Article
TY - JOUR
T1 - Self-assembled monolayer structures of hexadecylamine on Cu surfaces
T2 - Density-functional theory
AU - Liu, Shih Hsien
AU - Balankura, Tonnam
AU - Fichthorn, Kristen Ann
PY - 2016/1/1
Y1 - 2016/1/1
N2 - We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the (√3 × √3) R30° pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.
AB - We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the (√3 × √3) R30° pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.
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U2 - 10.1039/c6cp07030b
DO - 10.1039/c6cp07030b
M3 - Article
VL - 18
SP - 32753
EP - 32761
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 48
ER -