Effect of lattice topology on the adsorption of benzyl alcohol on kaolinite surfaces: Quantum chemical calculations of geometry optimization, binding energy, and NMR chemical shielding

Lee, Bum Han; Lee, Sung Keun

doi:10.2138/am.2009.3198

Cited by 16 publications

(14 citation statements)

References 71 publications

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“…The on-site electron-electron interactions were determined using the generalized gradient approximation (GGA)-based Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional [57]. The long-range order dispersion interactions, such as the van der Waals interaction, significantly influence the molecular crystal structures and cleaved surfaces with hydrogen bond-like long range interactions [58][59][60][61]. Accordingly, the hybrid semi-empirical dispersion correction term based on the Tkatchenko-Scheffler method was applied to the single-point energy calculations and the structure optimization calculations [58,59].…”

Section: Structure Optimization and Electronic Structure Calculationsmentioning

confidence: 99%

Atomistic View of Mercury Cycling in Polar Snowpacks: Probing the Role of Hg2+ Adsorption Using Ab Initio Calculations

Han

Lee

et al. 2019

Minerals

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Photochemical oxidation of atmospheric elemental mercury (Hg0) promotes reactive oxidized Hg (HgII) adsorption on particles and deposition to the polar snowpack. The deposited Hg either returns to the atmosphere via photochemical reduction or remains in the snowpack depending on the strength of adsorption. In this study, we performed ab initio calculations to understand the atomic-level cause of the fate of adsorbed Hg by determining the adsorption affinity for Hg2+, the simplest form of HgII, of barite, halite, muscovite, illite, and ice-Ih as potential adsorbents. The adsorption affinity was estimated by calculating the energy required to dissociate adsorbed Hg2+ from the adsorbents. The results reveal that Hg2+ is stable on the surfaces of the selected adsorbents, except barite, but is prone to photodissociation under solar ultraviolet radiation. This mild adsorption is expected to contribute to the bidirectional exchange of Hg between the atmosphere and the polar snowpack. Thus, this theoretical approach can provide complementary perspectives on polar Hg dynamics beyond the limitations of field and laboratory experiments. Further studies on more complicated and realistic adsorption models with different HgII species and adsorbent surfaces having diverse defective structures are required to better comprehend air–snow Hg cycling in the polar regions.

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Section: Structure Optimization and Electronic Structure Calculationsmentioning

confidence: 99%

Atomistic View of Mercury Cycling in Polar Snowpacks: Probing the Role of Hg2+ Adsorption Using Ab Initio Calculations

Han

Lee

et al. 2019

Minerals

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“…8 These authors proposed that non-bonded interactions may account for shifts 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 5 in IR bands. Furthermore, ab initio studies have recently explored the nature of the interaction at similar interfaces, such as organic monomers on kaolinite 10,11 and benzene and benzenediol on hydrophilic and hydrophobic silica surfaces. 12 These authors have put forward the predominant role of electrostatic interactions leading to physisorption.…”

Section: Figure 1 A) Typical Snapshots (Main and Insets) Of Modeled mentioning

confidence: 99%

Organic–Clay Interfacial Chemical Bonds Probed by ab Initio Calculations

et al. 2015

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Evaluating the nature of binding of the organic phase (called kerogen) with clays and other minerals in gas and oil shale is of critical importance for developing optimal processes for hydrocarbon extraction and recovery. Here we report the results of an ab initio reactive study of a gaseous oil/clay interface, which consists of grafting fragments of sp 3 methane and sp 2 benzene onto the basal surface of illite. Methane and benzene fragments were selected as they correspond to the simplest monomers of the immature (aliphatic sp 3 carbon atoms) and mature (aromatic sp 2 carbon atoms) stages of the kerogen macromolecule while illite is encountered in many shale formations. We find that the methyl or phenyl radicals always bond upright to one of the outmost Si atoms of the clay phase, while the H atom attaches to the inner Al-OH group forming a water molecule. The covalent attachment of the radicals to the oxygen atoms of the clay surface is always less favorable than to the silicon atoms. The energetics of these grafted adducts are discussed along with the maturation state of the shale.An unanticipated signature of the covalent Si-C binding is the formation of hypervalent Si complexes, characterized by elongated bonds at the oil/clay interface. We complement our atomistic modeling by simulating IR spectra of the two covalently grafted interfaces (methylillite and phenyl-illite) which fingerprint elongated Si-C bonds in the frequency range 1100 -1250 cm -1 . This novel finding should have a large impact on the understanding of fracking conditions in shales through this tight-and loose-bonded organic/inorganic interface.

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“…A larger mineral surface cluster was achieved using a molecular mechanics/quantum mechanics (QM/MM) hybrid calculation of acetate binding on a cluster model of kaolinite-type mineral surfaces [33]. More recently, periodic DFT methods have been used to study the binding of organic acids and larger hydrophobic molecules to mineral surfaces [16, [34][35][36][37][38][39][40], as well as the modeling of reactions of organic molecules at mineral surfaces, including decarboxylation of natural organic matter [16,41].…”

Section: Simulation Studies Of Organic-mineral Structuresmentioning

confidence: 99%

Interaction of Natural Organic Matter with Layered Minerals: Recent Developments in Computational Methods at the Nanoscale

2014

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Abstract:The role of mineral surfaces in the adsorption, transport, formation, and degradation of natural organic matter (NOM) in the biosphere remains an active research area owing to the difficulties in identifying proper working models of both NOM and mineral phases present in the environment. The variety of aqueous chemistries encountered in the subsurface (e.g., oxic vs. anoxic, variable pH) further complicate this field of study. Recently, the advent of nanoscale probes such as X-ray adsorption spectroscopy and surface vibrational spectroscopy applied to study such complicated interfacial systems have enabled new insight into NOM-mineral interfaces. Additionally, due to increasing capabilities in computational chemistry, it is now possible to simulate molecular processes of NOM at multiple scales, from quantum methods for electron transfer to classical methods for folding and adsorption of macroparticles. In this review, we present recent developments in interfacial properties of NOM adsorbed on mineral surfaces from a computational point of view that is informed by recent experiments.

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Effect of lattice topology on the adsorption of benzyl alcohol on kaolinite surfaces: Quantum chemical calculations of geometry optimization, binding energy, and NMR chemical shielding

Cited by 16 publications

References 71 publications

Atomistic View of Mercury Cycling in Polar Snowpacks: Probing the Role of Hg2+ Adsorption Using Ab Initio Calculations

Atomistic View of Mercury Cycling in Polar Snowpacks: Probing the Role of Hg2+ Adsorption Using Ab Initio Calculations

Organic–Clay Interfacial Chemical Bonds Probed by ab Initio Calculations

Interaction of Natural Organic Matter with Layered Minerals: Recent Developments in Computational Methods at the Nanoscale

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