Wettability of alkylated quartz surfaces is of primary importance in several technological applications, including the development of oil and gas reservoirs and carbon geo-sequestration. It is intuitively understood and experimentally confirmed that hydroxylated quartz surfaces are hydrophilic. By gradually saturating a hydroxylated (001) α-quartz surface with pentyl groups, we show using molecular dynamics simulations that the surface can also exhibit extreme hydrophobicity. Within a range of surface pentyl group density from 0.29 to 3.18/nm2, the contact angle of a water droplet under 10 MPa pressure of carbon dioxide at 300 K changes from 10–20 to 180°. This study has shown that a complete description of wettability of alkylated quartz surfaces requires three contact anglesone at the tip level of pentyl groups and two at the level of the quartz surface. The latter two are the contact angle of the spherical droplet and the hidden contact angle of a water “skirt” formed between the tip level of pentyl groups and the quartz surface. Analysis of the hidden contact angle unveils a binary wettability, where the surface relatively abruptly transforms from hydrophilic (the contact angle is less than 90°) to hydrophobic (the contact angle is 180°) with an increase in surface pentyl group concentration.

Bond formation and rearrangement reactions in gas phase electron attachment were studied through dissociative electron attachment (DEA) to pentafluorotoluene (PFT), pentafluoroaniline (PFA) and pentafluorophenol (PFP) in the energy range 0-14 eV. In the case of PFA and PFP, the dominant processes involve formation of [M - HF](-) through the loss of neutral HF. This fragmentation channel is most efficient at low incident electron energy and for PFP it is accompanied by a substantial conformational change of the anionic fragment. At higher energy, HF loss is also observed as well as a number of other fragmentation processes. Thermochemical threshold energies have been computed for all the observed fragments and classical trajectories of the electron attachment process were calculated to elucidate the fragmentation mechanisms. For the dominant reaction channel leading to the loss of HF from PFP, the minimum energy path was calculated using the nudged elastic band method.

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To extend applicability and to overcome limitations of combining rules for nonbond potential parameters, in this study, CLAYFF and DREIDING force fields are coupled at the level of atomic site charges to model quartz surfaces with chemisorpt hydrocarbons. Density functional theory and Bader charge analysis are applied to calculate charges of atoms of the OC bond connecting a quartz crystal and an alkyl group. The study demonstrates that the hydrogen atom of the quartz surface hydroxyl group can be removed and its charge can be redistributed among the oxygen and carbon atoms of the OC bond in a manner consistent with the results calculated at the density functional level of theory. Augmented with modified charges of the OC bond, force fields can then be applied to a practical problem of evaluation of the contact angle of a water droplet on alkylated quartz surfaces in a carbon dioxide environment, which is relevant for carbon geo-sequestration and in a broader context of oil and gas recovery. Alkylated quartz surfaces have been shown to be extremely hydrophobic even when the surface density of hydroxyl groups is close to the highest naturally observed density of 6.2 OH groups per square nanometer.