Department of Physical and Organic Chemistry, Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia.
Chemphyschem. 2011 Dec 23;12(18):3547-55. doi: 10.1002/cphc.201100537. Epub 2011 Nov 11.
The gas-phase adsorption of 1,2,3-triazole, benzotriazole, and naphthotriazole-considered as corrosion inhibitors-on copper surfaces was studied and characterized using density functional theory (DFT) calculations. We find that the molecule-surface bond strength increases with increasing molecular size, thus following the sequence: triazole<benzotriazole<naphthotriazole. This trend is explained in terms of molecular electronegativity and chemical hardness, which decrease monotonously as the molecular size increases. While the electronegativity of triazole is almost degenerate with the work function of Cu(111) surface, the electronegativity of larger acenotriazoles is smaller. The difference in electronegativity between the Cu(111) and the acenotriazoles thus increases with increasing the molecular size, which, together with decreasing the molecular hardness, results in larger molecule-to-metal electron charge transfer and stronger molecule-surface bonds.
采用密度泛函理论（DFT）计算研究了 1,2,3-三唑、苯并三唑和萘并三唑（作为腐蚀抑制剂）在铜表面的气相吸附。我们发现，分子-表面键合强度随分子尺寸的增加而增加，因此遵循以下顺序：三唑<苯并三唑<萘并三唑。这一趋势可以用分子电负性和化学硬度来解释，随着分子尺寸的增加，它们单调减小。虽然三唑的电负性几乎与 Cu(111)表面的功函数相等，但较大的 acenotriazoles 的电负性更小。因此，Cu(111)和 acenotriazoles 之间的电负性差异随着分子尺寸的增加而增加，这与分子硬度的降低一起导致了更大的分子到金属的电子电荷转移和更强的分子-表面键合。
