TY - JOUR

T1 - Intermolecular potentials for simulations of collisions of SiNCS + and (CH 3) 2SiNCS + ions with fluorinated self-assembled monolayers

AU - Nogueira, Juan José

AU - Sánchez-Coronilla, Antonio

AU - Marques, Jorge M.C.

AU - Hase, William L.

AU - Martínez-Núñez, Emilio

AU - Vázquez, Saulo A.

N1 - Funding Information:
J.J.N., E.M.-N. and S.V.R. thank the “Ministerio de Educación y Ciencia” (Grant No. CTQ2006-06301 ) and “Xunta de Galicia” (Grant No. PGDIT07PXIB209072PR and “Axuda para Consolidación e Estruturación de unidades de investigación competitivas do Sistema Universitario de Galicia, Xunta de Galicia 2007/050, cofinanciada polo FEDER 2007-2013”) for financial support. The contribution by W. L. Hase was supported by the National Science Foundation Partnership in International Research and Education (PIRE) Grant No. OISE-0730114 and the Robert A. Welch Foundation under Grant No. D-0005. The authors thank “Centro de Supercomputación de Galicia (CESGA)” for the use of its computational resources.

PY - 2012/5/3

Y1 - 2012/5/3

N2 - Analytical potential energy functions were developed for interactions of SiNCS + and (CH 3) 2SiNCS + ions with perfluorinated self-assembled monolayer (F-SAM) surfaces. Two model compounds were used to represent an F-SAM: CF 4 and nine chains of perfluorobutane forming a miniSAM structure. Density functional theory plus dispersion (DFT-D) calculations were carried out to compute intermolecular potential energy curves (IPECs) for these systems. The applied DFT-D method (specifically, B97-D) was successfully tested against high-level wavefunction calculations performed on the smallest system investigated. The IPECs calculated at the B97-D level were fitted to analytical potentials of the Buckingham type. The calculations show that the parameters obtained from the fits involving CF 4 are transferable to the miniSAM system, provided the fittings are conducted with caution, thus corroborating that CF 4 is a good model for parameterizing intermolecular potentials for interactions of gases with F-SAM surfaces.

AB - Analytical potential energy functions were developed for interactions of SiNCS + and (CH 3) 2SiNCS + ions with perfluorinated self-assembled monolayer (F-SAM) surfaces. Two model compounds were used to represent an F-SAM: CF 4 and nine chains of perfluorobutane forming a miniSAM structure. Density functional theory plus dispersion (DFT-D) calculations were carried out to compute intermolecular potential energy curves (IPECs) for these systems. The applied DFT-D method (specifically, B97-D) was successfully tested against high-level wavefunction calculations performed on the smallest system investigated. The IPECs calculated at the B97-D level were fitted to analytical potentials of the Buckingham type. The calculations show that the parameters obtained from the fits involving CF 4 are transferable to the miniSAM system, provided the fittings are conducted with caution, thus corroborating that CF 4 is a good model for parameterizing intermolecular potentials for interactions of gases with F-SAM surfaces.

KW - Analytical potentials

KW - Density functional theory plus dispersion (DFT-D)

KW - Intermolecular potential energy curves

KW - Perfluorinated self-assembled monolayer

KW - Silyl ions

UR - http://www.scopus.com/inward/record.url?scp=84861345896&partnerID=8YFLogxK

U2 - 10.1016/j.chemphys.2011.02.014

DO - 10.1016/j.chemphys.2011.02.014

M3 - Article

AN - SCOPUS:84861345896

VL - 399

SP - 193

EP - 204

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

ER -