Theoretical study of the structure of self-assembled monolayers of short alkylthiolates on Au(111) and Ag(111): the role of induced substrate reconstruction and chain-chain interactions

被引:22
作者
Abufager, P. N. [1 ,2 ]
Solano Canchaya, J. G. [1 ,2 ]
Wang, Y. [3 ]
Alcami, M. [3 ]
Martin, F. [3 ,4 ]
Alvarez Soria, L. [5 ,6 ]
Martiarena, M. L. [5 ,6 ]
Reuter, K. [7 ]
Busnengo, H. F. [1 ,2 ]
机构
[1] Univ Nacl Rosario, Lab Colis Atom, Fac Ciencias Exactas Ingn & Agrimensura, RA-2000 Rosario, Argentina
[2] Consejo Nacl Invest Cient & Tecn, Inst Fis Rosario, RA-2000 Rosario, Argentina
[3] Univ Autonoma Madrid, Dept Quim C13, E-28049 Madrid, Spain
[4] Inst Madrileno Estudios Avanzados Nanociencia IMD, Madrid 28049, Spain
[5] Ctr Atom Bariloche, RA-8400 San Carlos De Bariloche, Argentina
[6] Inst Balseiro, RA-8400 San Carlos De Bariloche, Argentina
[7] Tech Univ Munich, Dept Chem, D-85747 Garching, Germany
关键词
DENSITY-FUNCTIONAL THEORY; COINAGE METAL-SURFACES; INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; AUGMENTED-WAVE METHOD; ALKANETHIOL MONOLAYERS; ORGANIC-SURFACES; ROOM-TEMPERATURE; SILVER SURFACES; ION-SCATTERING;
D O I
10.1039/c0cp02490b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We compare the stability of various structures of high coverage self-assembled monolayers (SAMs) of short alkylthiolates, S(CH2)(n-1)CH3 (= C-n), on Ag(111) and Au(111). We employ: (i) the ab initio thermodynamics approach based on density functional theory (DFT) calculations, to compare the stability of SAMs of C-1 (with coverages Theta = 3/7 and 1/3) on both substrates, and (ii) a set of pairwise interatomic potentials derived from second-order Moller-Plesset (MP2) perturbation theory calculations, to estimate the role of chain-chain (Ch-Ch) interactions in the structure and stability of SAMs of longer chain alkylthiolates. For C-1/Ag(111) (C-1/Au(111)) the SAM with Theta = 3/7 is more (less) stable than for Theta = 1/3 in a wide range of temperatures and pressures in line with experiments. In addition, for the molecular densities of SAMs corresponding to Theta = 3/7 and 1/3, the MP2-based Ch-Ch interaction potential also predicts the different chain orientations observed experimentally in SAMs of alkylthiolates on Ag(111) and Au(111). Thus, for short length alkylthiolates, a simple model based on first principles calculations that separately accounts for molecule-surface (M-S) and Ch-Ch interactions succeeds in predicting the main structural differences between the full coverage SAMs usually observed experimentally on Ag(111) and Au(111).
引用
收藏
页码:9353 / 9362
页数:10
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