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1D self-assembly of chemisorbed thymine on Cu(110) driven by dispersion forces.

Temprano, I; Thomas, G; Haq, S; Dyer, M S; Latter, E G; Darling, G R; Uvdal, Per LU and Raval, R (2015) In Journal of Chemical Physics 142(10).
Abstract
Adsorption of thymine on a defined Cu(110) surface was studied using reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and scanning tunnelling microscopy (STM). In addition, density functional theory (DFT) calculations were undertaken in order to further understand the energetics of adsorption and self-assembly. The combination of RAIRS, TPD, and DFT results indicates that an upright, three-point-bonded adsorption configuration is adopted by the deprotonated thymine at room temperature. DFT calculations show that the upright configuration adopted by individual molecules arises as a direct result of strong O-Cu and N-Cu bonds between the molecule and the surface. STM data reveal that this upright... (More)
Adsorption of thymine on a defined Cu(110) surface was studied using reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and scanning tunnelling microscopy (STM). In addition, density functional theory (DFT) calculations were undertaken in order to further understand the energetics of adsorption and self-assembly. The combination of RAIRS, TPD, and DFT results indicates that an upright, three-point-bonded adsorption configuration is adopted by the deprotonated thymine at room temperature. DFT calculations show that the upright configuration adopted by individual molecules arises as a direct result of strong O-Cu and N-Cu bonds between the molecule and the surface. STM data reveal that this upright thymine motif self-assembles into 1D chains, which are surprisingly oriented along the open-packed [001] direction of the metal surface and orthogonal to the alignment of the functional groups that are normally implicated in H-bonding interactions. DFT modelling of this system reveals that the molecular organisation is actually driven by dispersion interactions, which cause a slight tilt of the molecule and provide the major driving force for assembly into dimers and 1D chains. The relative orientations and distances of neighbouring molecules are amenable for π-π stacking, suggesting that this is an important contributor in the self-assembly process. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
142
issue
10
publisher
American Institute of Physics
external identifiers
  • pmid:25770505
  • wos:000350978000017
  • scopus:84923771082
ISSN
0021-9606
DOI
10.1063/1.4907721
language
English
LU publication?
yes
id
3bd14e21-860f-4d7f-bd81-ed74aedf4d2b (old id 5258661)
date added to LUP
2015-04-16 13:40:01
date last changed
2017-04-30 04:31:44
@article{3bd14e21-860f-4d7f-bd81-ed74aedf4d2b,
  abstract     = {Adsorption of thymine on a defined Cu(110) surface was studied using reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and scanning tunnelling microscopy (STM). In addition, density functional theory (DFT) calculations were undertaken in order to further understand the energetics of adsorption and self-assembly. The combination of RAIRS, TPD, and DFT results indicates that an upright, three-point-bonded adsorption configuration is adopted by the deprotonated thymine at room temperature. DFT calculations show that the upright configuration adopted by individual molecules arises as a direct result of strong O-Cu and N-Cu bonds between the molecule and the surface. STM data reveal that this upright thymine motif self-assembles into 1D chains, which are surprisingly oriented along the open-packed [001] direction of the metal surface and orthogonal to the alignment of the functional groups that are normally implicated in H-bonding interactions. DFT modelling of this system reveals that the molecular organisation is actually driven by dispersion interactions, which cause a slight tilt of the molecule and provide the major driving force for assembly into dimers and 1D chains. The relative orientations and distances of neighbouring molecules are amenable for π-π stacking, suggesting that this is an important contributor in the self-assembly process.},
  articleno    = {101916},
  author       = {Temprano, I and Thomas, G and Haq, S and Dyer, M S and Latter, E G and Darling, G R and Uvdal, Per and Raval, R},
  issn         = {0021-9606},
  language     = {eng},
  number       = {10},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {1D self-assembly of chemisorbed thymine on Cu(110) driven by dispersion forces.},
  url          = {http://dx.doi.org/10.1063/1.4907721},
  volume       = {142},
  year         = {2015},
}