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Cyanide adsorbed on coinage metal electrodes: A relativistic density functional investigation
Author(s) -
Liao MengSheng,
Lü Xin,
Zhang QianEr
Publication year - 1998
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1998)67:3<175::aid-qua4>3.0.co;2-s
Subject(s) - cyanide , electrode , metal , adsorption , density functional theory , chemistry , chemical physics , inorganic chemistry , materials science , computational chemistry , organic chemistry
The adsorptive properties of cyanide (CN − ) on coinage metal (M) electrodes (M=Cu, Ag, Au) have been investigated using a relativistic density functional method. The way to model the electrochemical potential applied to the electrodes is to consider the systems in the presence of a perturbative external field F . The field‐perturbative approach is proven to be a suitable method in interpreting the observed spectral shifts with electrode potential. The calculated potential‐dependent shifts of ω M(SINGLE BOND)CN and ω C(SINGLE BOND)M are similar for the three metals, in agreement with experiment observations. The relativistic effects are required to account for the similarity in the frequency shifts of ω M(SINGLE BOND)CN . The calculated vibrational tuning rates d ω C(SINGLE BOND)N / dF are 6.61×10 −7 , 6.61×10 −7 , and 5.64×10 −7 cm −1 /(V/cm) for M=Cu, Ag, and Au, respectively. The coupling of the M(SINGLE BOND)CN and C(SINGLE BOND)N internal modes contributes significantly (about 25%) to the size of the frequency shifts Δω C(SINGLE BOND)N of the ligand. The effect of electric fields on the metal(SINGLE BOND)CN − bonding is also investigated. It is shown that changes in the magnitude of CN − to the metal donation and M(SINGLE BOND)CN bond strength occur under the influence of the electric field. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 175–185, 1998