Chain-length and temperature dependence of self-assembled monolayers of alkylthiolates on Au(111) and Ag(111) surfaces

Y Wang; J G Solano Canchaya; W Dong; M Alcamí; H F Busnengo; F Martín

doi:10.1021/jp412285v

Chain-length and temperature dependence of self-assembled monolayers of alkylthiolates on Au(111) and Ag(111) surfaces

J Phys Chem A. 2014 Jun 12;118(23):4138-46. doi: 10.1021/jp412285v. Epub 2014 Jun 2.

Authors

Y Wang¹, J G Solano Canchaya, W Dong, M Alcamí, H F Busnengo, F Martín

Affiliation

¹ Departamento de Química Módulo 13, Universidad Autónoma de Madrid , 28049 Madrid, Spain.

PMID: 24856824
DOI: 10.1021/jp412285v

Abstract

We present a molecular dynamics (MD) study on the structure of self-assembled monolayers (SAMs) of alkylthiolates on various metal surfaces, with especial attention to Au(111) and Ag(111). Variations in the structure of these SAMs as a function of temperature and alkyl-chain length are systematically investigated. The MD simulations are performed by using a recently developed force field based on second-order Møller-Plesset perturbation theory calculations. Good agreement between the present results and the existing experimental data is found on Au(111). On Ag(111) the comparison between theory and experiment is also satisfactory for alkylthiolates with no more than 14 carbon atoms. The dependences of the average tilt angle of SAMs on temperature and chain length are easily understood by means of a simple single-chain model.