### Abstract

Analytical potential energy functions were developed for interactions of SiNCS ^{+} and (CH _{3}) _{2}SiNCS ^{+} 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.

Original language | English |
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Pages (from-to) | 193-204 |

Number of pages | 12 |

Journal | Chemical Physics |

Volume | 399 |

DOIs | |

State | Published - May 3 2012 |

### Keywords

- Analytical potentials
- Density functional theory plus dispersion (DFT-D)
- Intermolecular potential energy curves
- Perfluorinated self-assembled monolayer
- Silyl ions

## Fingerprint Dive into the research topics of 'Intermolecular potentials for simulations of collisions of SiNCS <sup>+</sup> and (CH <sub>3</sub>) <sub>2</sub>SiNCS <sup>+</sup> ions with fluorinated self-assembled monolayers'. Together they form a unique fingerprint.

## Cite this

^{+}and (CH

_{3})

_{2}SiNCS

^{+}ions with fluorinated self-assembled monolayers.

*Chemical Physics*,

*399*, 193-204. https://doi.org/10.1016/j.chemphys.2011.02.014