Benzotriazole adsorption on Cu 2O(111) surfaces

A first-principles study

Yong Jiang, James Adams, Donghai Sun

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

The adsorption of benzotriazole (BTAH) on Cu 2O(111) was investigated with use of first-principles density functional theory calculations. Two possible adsorption structures were considered for both one-quarter and full adsorption coverage. We found that BTAH strongly chemisorbs (1.2-1.5 eV) onto Cu 2U(111) by forming a chemical bond with a surface copper atom through nitrogen sp 2 lone pairs, and a hydrogen bond with a surface oxygen atom through a C-H or N-H proton. The chemical interaction between the surface copper site and the molecule is the combined effect of a strong lone-pair → hybrid Cu-d z2sp z σ-donation and a relatively weak d yz → 6π* back-donation. Vibration calculations were carried out to predict the BTAH-Cu 2O stretching frequencies for both adsorption structures. The calculated stretching frequency (381 and 428 cm -1) could overlap with the BTAH benzene-ring torsion band. An estimate for the BTAH-Cu vibrational frequency (226 and 223.4 cm -1 for two adsorption modes, respectively) is in good agreement with an experimentally observed Raman peak of 240 cm -1.

Original languageEnglish (US)
Pages (from-to)12851-12857
Number of pages7
JournalJournal of Physical Chemistry B
Volume108
Issue number34
DOIs
StatePublished - Aug 26 2004

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Adsorption
adsorption
Stretching
Copper
copper
Atoms
Hydrogen
Chemical bonds
Vibrational spectra
chemical bonds
Benzene
Torsional stress
nitrogen atoms
torsion
Density functional theory
Protons
oxygen atoms
Hydrogen bonds
Nitrogen
benzene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Benzotriazole adsorption on Cu 2O(111) surfaces : A first-principles study. / Jiang, Yong; Adams, James; Sun, Donghai.

In: Journal of Physical Chemistry B, Vol. 108, No. 34, 26.08.2004, p. 12851-12857.

Research output: Contribution to journalArticle

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N2 - The adsorption of benzotriazole (BTAH) on Cu 2O(111) was investigated with use of first-principles density functional theory calculations. Two possible adsorption structures were considered for both one-quarter and full adsorption coverage. We found that BTAH strongly chemisorbs (1.2-1.5 eV) onto Cu 2U(111) by forming a chemical bond with a surface copper atom through nitrogen sp 2 lone pairs, and a hydrogen bond with a surface oxygen atom through a C-H or N-H proton. The chemical interaction between the surface copper site and the molecule is the combined effect of a strong lone-pair → hybrid Cu-d z2sp z σ-donation and a relatively weak d yz → 6π* back-donation. Vibration calculations were carried out to predict the BTAH-Cu 2O stretching frequencies for both adsorption structures. The calculated stretching frequency (381 and 428 cm -1) could overlap with the BTAH benzene-ring torsion band. An estimate for the BTAH-Cu vibrational frequency (226 and 223.4 cm -1 for two adsorption modes, respectively) is in good agreement with an experimentally observed Raman peak of 240 cm -1.

AB - The adsorption of benzotriazole (BTAH) on Cu 2O(111) was investigated with use of first-principles density functional theory calculations. Two possible adsorption structures were considered for both one-quarter and full adsorption coverage. We found that BTAH strongly chemisorbs (1.2-1.5 eV) onto Cu 2U(111) by forming a chemical bond with a surface copper atom through nitrogen sp 2 lone pairs, and a hydrogen bond with a surface oxygen atom through a C-H or N-H proton. The chemical interaction between the surface copper site and the molecule is the combined effect of a strong lone-pair → hybrid Cu-d z2sp z σ-donation and a relatively weak d yz → 6π* back-donation. Vibration calculations were carried out to predict the BTAH-Cu 2O stretching frequencies for both adsorption structures. The calculated stretching frequency (381 and 428 cm -1) could overlap with the BTAH benzene-ring torsion band. An estimate for the BTAH-Cu vibrational frequency (226 and 223.4 cm -1 for two adsorption modes, respectively) is in good agreement with an experimentally observed Raman peak of 240 cm -1.

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