Adsorption of formate species on Cu(h,k,l) low index surfaces

Arunabhiram Chutia; Ian P. Silverwood; Matthew R. Farrow; David O. Scanlon; Peter P. Wells; Michael Bowker; Stewart F. Parker; C. Richard A. Catlow

doi:10.1016/j.susc.2016.05.002

Adsorption of formate species on Cu(h,k,l) low index surfaces

Arunabhiram Chutia^*, Ian P. Silverwood, Matthew R. Farrow, David O. Scanlon, Peter P. Wells, Michael Bowker, Stewart F. Parker, C. Richard A. Catlow

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We report a density functional theory study on the relative stability of formate species on Cu(h,k,l) low index surfaces using a range of exchange-correlation functionals. We find that these functionals predict similar geometries for the formate molecule adsorbed on the Cu surface. A comparison of the calculated vibrational transition energies of a perpendicular configuration of formate on Cu surface shows an excellent agreement with the experimental spectrum obtained from inelastic neutron spectroscopy. From the calculations on adsorption energy we find that formate is most stable on the Cu(110) surface as compared to Cu(111) and Cu(100) surfaces. Bader analysis shows that this feature could be related to the higher charge transfer from the Cu(110) surface and optimum charge density at the interfacial region due to bidirectional electron transfer between the formate and the Cu surface. Analysis of the partial density of states finds that in the -5.5 eV to -4.0 eV region, hybridization between O p and the non-axial Cu d_yz and d_xz orbitals takes place on the Cu(110) surface, which is energetically more favourable than on the other surfaces.

Original language	English
Pages (from-to)	45-54
Number of pages	10
Journal	Surface Science
Volume	653
DOIs	https://doi.org/10.1016/j.susc.2016.05.002
Publication status	Published - 1 Nov 2016

Bibliographical note

Funding Information:
Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC ( EP/L000202 ), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ). The STFC Rutherford Appleton Laboratory is thanked for access to neutron beam facilities. The UK Catalysis Hub is thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (grants EP/K014706/1 , EP/K014668/1 , EP/K014854/1 , EP/K014714/1 and EP/M013219/1 ).

Publisher Copyright:
© 2016 The Authors.

Keywords

Charge transfer
Density functional theory
Formate stability
Hybridization
Inelastic neutron scattering spectroscopy
Non-axial Cu d-orbital

ASJC Scopus subject areas

Condensed Matter Physics
Surfaces and Interfaces
Surfaces, Coatings and Films
Materials Chemistry

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10.1016/j.susc.2016.05.002

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@article{b5633b1eac2348149936c1f45dfef0bb,

title = "Adsorption of formate species on Cu(h,k,l) low index surfaces",

abstract = "We report a density functional theory study on the relative stability of formate species on Cu(h,k,l) low index surfaces using a range of exchange-correlation functionals. We find that these functionals predict similar geometries for the formate molecule adsorbed on the Cu surface. A comparison of the calculated vibrational transition energies of a perpendicular configuration of formate on Cu surface shows an excellent agreement with the experimental spectrum obtained from inelastic neutron spectroscopy. From the calculations on adsorption energy we find that formate is most stable on the Cu(110) surface as compared to Cu(111) and Cu(100) surfaces. Bader analysis shows that this feature could be related to the higher charge transfer from the Cu(110) surface and optimum charge density at the interfacial region due to bidirectional electron transfer between the formate and the Cu surface. Analysis of the partial density of states finds that in the -5.5 eV to -4.0 eV region, hybridization between O p and the non-axial Cu dyz and dxz orbitals takes place on the Cu(110) surface, which is energetically more favourable than on the other surfaces.",

keywords = "Charge transfer, Density functional theory, Formate stability, Hybridization, Inelastic neutron scattering spectroscopy, Non-axial Cu d-orbital",

author = "Arunabhiram Chutia and Silverwood, {Ian P.} and Farrow, {Matthew R.} and Scanlon, {David O.} and Wells, {Peter P.} and Michael Bowker and Parker, {Stewart F.} and Catlow, {C. Richard A.}",

note = "Funding Information: Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC ( EP/L000202 ), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ). The STFC Rutherford Appleton Laboratory is thanked for access to neutron beam facilities. The UK Catalysis Hub is thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (grants EP/K014706/1 , EP/K014668/1 , EP/K014854/1 , EP/K014714/1 and EP/M013219/1 ). Publisher Copyright: {\textcopyright} 2016 The Authors.",

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doi = "10.1016/j.susc.2016.05.002",

language = "English",

volume = "653",

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T1 - Adsorption of formate species on Cu(h,k,l) low index surfaces

AU - Chutia, Arunabhiram

AU - Silverwood, Ian P.

AU - Farrow, Matthew R.

AU - Scanlon, David O.

AU - Wells, Peter P.

AU - Bowker, Michael

AU - Parker, Stewart F.

AU - Catlow, C. Richard A.

N1 - Funding Information: Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC ( EP/L000202 ), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ). The STFC Rutherford Appleton Laboratory is thanked for access to neutron beam facilities. The UK Catalysis Hub is thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (grants EP/K014706/1 , EP/K014668/1 , EP/K014854/1 , EP/K014714/1 and EP/M013219/1 ). Publisher Copyright: © 2016 The Authors.

PY - 2016/11/1

Y1 - 2016/11/1

N2 - We report a density functional theory study on the relative stability of formate species on Cu(h,k,l) low index surfaces using a range of exchange-correlation functionals. We find that these functionals predict similar geometries for the formate molecule adsorbed on the Cu surface. A comparison of the calculated vibrational transition energies of a perpendicular configuration of formate on Cu surface shows an excellent agreement with the experimental spectrum obtained from inelastic neutron spectroscopy. From the calculations on adsorption energy we find that formate is most stable on the Cu(110) surface as compared to Cu(111) and Cu(100) surfaces. Bader analysis shows that this feature could be related to the higher charge transfer from the Cu(110) surface and optimum charge density at the interfacial region due to bidirectional electron transfer between the formate and the Cu surface. Analysis of the partial density of states finds that in the -5.5 eV to -4.0 eV region, hybridization between O p and the non-axial Cu dyz and dxz orbitals takes place on the Cu(110) surface, which is energetically more favourable than on the other surfaces.

AB - We report a density functional theory study on the relative stability of formate species on Cu(h,k,l) low index surfaces using a range of exchange-correlation functionals. We find that these functionals predict similar geometries for the formate molecule adsorbed on the Cu surface. A comparison of the calculated vibrational transition energies of a perpendicular configuration of formate on Cu surface shows an excellent agreement with the experimental spectrum obtained from inelastic neutron spectroscopy. From the calculations on adsorption energy we find that formate is most stable on the Cu(110) surface as compared to Cu(111) and Cu(100) surfaces. Bader analysis shows that this feature could be related to the higher charge transfer from the Cu(110) surface and optimum charge density at the interfacial region due to bidirectional electron transfer between the formate and the Cu surface. Analysis of the partial density of states finds that in the -5.5 eV to -4.0 eV region, hybridization between O p and the non-axial Cu dyz and dxz orbitals takes place on the Cu(110) surface, which is energetically more favourable than on the other surfaces.

KW - Charge transfer

KW - Density functional theory

KW - Formate stability

KW - Hybridization

KW - Inelastic neutron scattering spectroscopy

KW - Non-axial Cu d-orbital

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DO - 10.1016/j.susc.2016.05.002

M3 - Article

AN - SCOPUS:84974725327

SN - 0039-6028

VL - 653

SP - 45

EP - 54

JO - Surface Science

JF - Surface Science

ER -

Adsorption of formate species on Cu(h,k,l) low index surfaces

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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