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Of all publications in the section: 22
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Article
Skorokhodov E. S., Zhidomirov G.M., Eltsov K.N. et al. The Journal of Physical Chemistry C. 2019. Vol. 123. No. 32. P. 19806-19811.

The homoepitaxial growth of Si on Si(100) covered by a resist mask is a necessary technological step for the fabrication of donor-based quantum devices with scanning tunneling microscope lithography. In the present work, the chlorine monolayer is selected as the resist. Using density functional theory, we investigated the adsorption of a single silicon atom on Si(100)-2 × 1-Cl as the starting process of Si epitaxy. The incorporation of a silicon atom under a Cl monolayer proved to be the most energetically favorable process. Our results show that chlorine segregates on the surface during Si deposition and does not incorporate into homoepitaxial layers. In addition, we found that SiCl2*, SiCl3*, and SiCl4* clusters can be formed above a Si(100)-2 × 1-Cl surface while Si is adsorbed. SiCl2* clusters are bound weakly to the substrate, and their desorption leaves the silicon surface free of chlorine. To check whether the Si epitaxy is possible on the chlorine resist, we compare our results with the well-studied case of a hydrogen resist. We find the two processes to be similar; moreover, epitaxy on chlorine resist appears to have an advantage.

Added: Oct 25, 2019
Article
Nikitenko V. R., Saunina A. Y., A.P. Tyutnev et al. The Journal of Physical Chemistry C. 2017. Vol. 121. P. 7776-7781.

An analytic model for the field dependence of charge mobility is developed within the long-range-correlated disorder model of a dipole glass. Release of a charge carrier from a deep state is considered as hopping drift and diffusion in a quasi-Coulomb potential well. The analytic results, containing only one numerical parameter obtained from independent simulation, are in good agreement with the fit to the Monte-Carlo simulations. The developed approach justifies applicability of the concept of the effective transport level for the modeling of organic materials with large molecular dipoles.

Added: Oct 13, 2017
Article
Novikov S. V. The Journal of Physical Chemistry C. 2018. Vol. 122. P. 22856-22863.

We present a simple model of the bimolecular charge carrier recombination in polar amorphous organic semiconductors in which the dominant part of the energetic disorder is provided by permanent dipoles and show that the recombination rate constant could be much smaller than the corresponding Langevin rate constant. The reason for the strong decrease of the rate constant is the long-range spatial correlation of the random energy landscape in amorphous dipolar materials; without spatial correlation, even strong disorder does not modify the Langevin rate constant. Our study shows that the signi fi cant suppression of the bimolecular recombination could take place in homogeneous amorphous organic semiconductors and does not need large-scale inhomogeneity of the material.

Added: Oct 15, 2018
Article
Ikhsanov R., Novitsky A., Protsenko I. E. et al. The Journal of Physical Chemistry C. 2018. Vol. 122. No. 22. P. 11985-11992.

We elaborate a semi-analytical model for calculation of the bulk internal emission of photoelectrons from metal nanoparticles into a semiconductor matrix. We introduce important effects in the model as the jump of the effective electron mass at the metal–semiconductor interface and cooling of the hot electrons because of electron–electron and electron–nanoparticle surface collisions in the metal. We study the interplay between the plasmonic electric dipole and quadrupole resonances and reveal the optimum parameters for different geometrical shapes of nanoparticles with respect to the photoemission cross section. We find that the absorption cross section well-predicts the optimum size of the dipolar nanoparticle. This opens the possibility for the fast optimization and design of the photoelectric devices.

Added: May 24, 2018
Article
Loganathan N., Yazaydin A. O., Bowers G. M. et al. The Journal of Physical Chemistry C. 2016. Vol. 120. P. 12429-12439.

The incorporation of Ca(2+) into smectite minerals is well-known to have a significant effect on the swelling behavior and mechanical properties of this environmentally and technologically important group of materials. Relative to common alkali cations such as Na+, K+, and Cs+, Ca(2+) has a larger charge/ionic radius ratio and thus interacts very differently with interlayer water molecules and the oxygens of the clay basal surface. Recent (2)H and (43)Ca NMR studies of the smectite mineral, hectorite, show that the molecular scale interlayer dynamics is quite different with Ca(2+) than with alkali cations. Classical molecular dynamics (MD) simulations presented here use a newly developed hectorite model with a disordered distribution of Li+/Mg(2+) substitutions in the octahedral sheet and provide new insight into the origin of the effects of Ca(2+) on the structure, dynamics, and energetics of smectite interlayers. The computed basal spacings and thermodynamic properties suggest the potential for formation of stable monolayer hydrates that have partial and complete water contents, a bilayer hydrate, and possible expansion to higher hydration states. The system hydration energies are comparable to those previously calculated for Ca–montmorillonite and are more negative than for Cs+ and N+ hectorite due to the higher hydration energy of Ca(2+). The coordination environments of Ca(2+) change significantly with increasing interlayer hydration, with the extent of coordination to basal oxygens decreasing as the number of interlayer molecules increases. On external (001) surfaces, the H2O molecules closest to the surface are adsorbed at the centers of ditrigonal cavities and bridge Ca(2+) to the surface. The Ca(2+) ions on the external surface are all in outer-sphere coordination with the basal oxygens of the surface, and the proximity-restricted region with a significant number of Ca(2+) is approximately 6 Šthick. Quantification of these interactions provides a basis for understanding intercalation of Ca(2+) by organic species and smectite minerals.

Added: Apr 30, 2017
Article
Loganathan N., Bowers G. M., Yazaydin A. O. et al. The Journal of Physical Chemistry C. 2018. Vol. 122. No. 8. P. 4391-4402.

In situ XRD and NMR experiments combined with molecular dynamics simulations using the grand canonical ensemble (GCMD) show that cation size, charge and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical CO2 under conditions relevant to the earth’s upper crust, petroleum reservoirs, and geological CO2 sequestration conditions (323 K and 90 bar). The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with relatively small ionic radii and high solvation and hydration energies (e.g., Li+, Na+ Mg2+, and Ca2+) does not intercalate dry CO2 and that the fully collapsed interlayer structure is the energetically most stable configuration. With increasing cation size and decreasing cation solvation energy, the energy barrier to CO2 intercalation decreases. With K+, Rb+, Cs+, Sr2+, and Ba2+ the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+ there is not even an energy barrier for CO2 intercalation, in agreement with the experimental XRD and NMR results that show clay layer expansion and CO2 incorporation. The number of intercalated CO2 molecules decreases with increasing size of the alkali cation but does not vary with ion size for the alkaline earth cations. 13C NMR spectroscopy and the GCMD simulations show that the average orientation of the intercalated CO2 molecules is with their O-C-O axes parallel to the basal clay surface and that they undergo a combination of rapid rotation about an axis perpendicular to the main molecular axis and wobbling motion with respect to the basal surface. Incorporation of CO2 in the interlayer decreases the coordination of Cs+ by the oxygen atoms of the basal surfaces, which is compensated by CO2 molecules entering their solvation shell, as predicted based on previously published NMR results. The GCMD simulations show that the strength of the interaction between the exchangeable cation and the clay structure dominates the intercalation energetics in dry scCO2. With relatively small cations, the cation-clay interactions outcompete cation solvation by CO2 molecules. The computed residence times for coordination among of interlayer species are consistent with the computed energetics.

Added: May 31, 2018
Article
Loganathan N., Bowers G. M., Yazaydin A. O. et al. The Journal of Physical Chemistry C. 2018. Vol. 122. No. 41. P. 23460-23469.

The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological C-sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using Grand Canonical Molecular Dynamics (GCMD) methods. The results show that the intercalation behavior is greatly different with cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than with cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+ the presence of a sub-monolayer of H2O is required for CO2 intercalation. The computational results provide detailed structural, dynamical and energetic insight into the differences in intercalation behavior and are in excellent agreement with in situ experimental XRD, IR, quartz crystal microbalance, and NMR results for smectite materials obtained under reservoir conditions.

Added: Oct 20, 2018
Article
Korsun O. M., Kalugin O. N., Vasenko A. S. et al. The Journal of Physical Chemistry C. 2016. Vol. 120. No. 46. P. 26514-26521.

The influence of bare and solvated cations imbedded inside single-walled carbon nanotubes (SWCNTs) on the SWCNT electronic properties is studied by ab initio electronic structure calculations. The roles of ion charge and ion solvation are investigated by comparing Li+ vs Mg2+ and Li+ vs its solvatocomplex with two ethylene carbonate (EC) molecules, [Li(EC)2]+. Two achiral nanotubes with similar radii but different electronic structure are considered, namely, the metallic, (15,15) armchair, and semiconducting, (26,0) zigzag, SWCNTs. The intercalation process is energetically favorable for both CNT topologies, with all bare cations and the solvatocomplex under investigation, with the doubly charged Mg2+ ion exhibiting the highest energy gain. Insertion of the bare ions into the SWCNTs increases the electronic entropy. The electronic entropy changes because the ions introduce new energy levels near the Fermi level. Those initially empty levels of the cations accept electron density and generate electronic holes in the valence band of both SWCNT topologies. As a consequence, the semiconducting (26,0) zigzag SWCNT becomes metallic, exhibiting hole conductivity. Solvation of the bare Li+ ion by EC molecules completely screens the influence of the ion charge on the SWCNT electronic properties, independent of the topology. The last fact validates the common practice of employing standard, nonpolarizable force field models in classical molecular dynamics simulations of electrolyte solutions interacting with CNTs. The strong dependence of the nanotube electronic properties on the presence of bare ions can be used for development of novel cation sensors for mass spectroscopy applications.

Added: Nov 22, 2016
Article
Novikov S. V. The Journal of Physical Chemistry C. 2019. Vol. 123. No. 31. P. 18854-18860.

We consider the bimolecular charge carrier recombination in amorphous organic semiconductors having a special kind of energetic disorder where energy levels for electrons and holes at a given transport site move in the same direction with the variation of some disorder governing parameter (the parallel disorder). This particular kind of  disorder could be found in materials where the dominant part of the energetic disorder is provided by the conformational disorder. Contrary to the recently studied case of electrostatic disorder, the conformational disorder, if spatially correlated,  leads to the increase of the recombination rate constant which becomes greater than the corresponding Langevin rate constant. Probably, organic semiconductors with the dominating conformational disorder represent the first class of amorphous organic semiconductors where the recombination rate constant could overcome the Langevin limit.

 

Added: Oct 24, 2019
Article
T.V. Pavlova, B. V. Andryushechkin, G.M. Zhidomirov. The Journal of Physical Chemistry C. 2016. Vol. 120. No. 5. P. 2829-2836.

First-principle density-functional calculations have been applied to study the interaction of molecular chlorine with the (111) plane of copper. Using transition-state search method, we considered the elementary processes (Cl2 dissociation, adsorption, diffusion, association, and desorption) on the chlorinated Cu(111) surface. A systematic study of possible desorption pathways has been carried out for different species (Cl, Cl2, CuCl, CuCl2, and Cu) at various chlorine coverage. As a result, we concluded that chlorine monolayer irrespective of the coverage desorbs in the form of CuCl molecules from step edges.

Added: Feb 26, 2018
Article
T.V. Pavlova, G.M. Zhidomirov, K.N. Eltsov. The Journal of Physical Chemistry C. 2018. Vol. 122. No. 3. P. 1741-1745.

This paper presents a density functional theory study for phosphine adsorption on a Si(001)-2 × 1 surface covered by a chlorine monolayer, including adsorption on local defects, i.e., mono- and bivacancies in the adsorbate layer (Cl, Cl2), and combined vacancies with removed silicon atoms (SiCl, SiCl2). Activation barriers were found for the adsorbing PH3 to dissociate into PH2 + H and PH + H2 fragments; it was also established that phosphine dissociation on combined vacancies is possible at room temperature. If there is a silicon vacancy on the surface, phosphorus settles in the Si(001) lattice as PH (if the vacancy is SiCl) or as PH2 (if the vacancy is SiCl2). This paper suggests a method to plant a separate phosphorus atom into the silicon surface layer with atomic precision, using phosphine adsorption on defects specially created on a Si(001)-2 × 1–Cl surface with a scanning tunneling microscope tip.

Added: Jan 10, 2019
Article
Komarov N., Tatiana V. Pavlova, Boris V. Andryushechkin. The Journal of Physical Chemistry C. 2019. Vol. 123. No. 45. P. 27659-27665.

Scanning tunneling microscopy (STM), lowenergy electron diffraction (LEED), Auger electron spectroscopy (AES) and density functional theory (DFT) calculations have been used to investigate the I2 adsorption on the Ni(110) surface. Dissociative adsorption takes place rapidly to form a c(2×2) layer at iodine coverage of 0.5 ML. DFT calculations show that hollow sites are energetically preferable for iodine adsorption on the Ni(110) surface. Increase of iodine coverage above 0.5 ML leads to the commensurate-incommensurate phase transition via nucleation of loops of domain-walls and to their subsequent ordering into the striped superstructure. At saturation, a striped domain-wall phase degenerates into the uniaxially compressed quasi-hexagonal phase. Further iodine dosing leads to the nucleation and growth of 2D nickel iodide islands.

Added: Oct 25, 2019
Article
Khan M., Nikitenko V., Tyutnev A. P. et al. The Journal of Physical Chemistry C. 2019. Vol. 3. No. 123. P. 1653-1659.

ABSTRACT: An analytic model based on the transport level and effective temperature concepts has been developed to describe consistently both the quasi- and nonequilibrium transport regimes in nonpolar organic solids with the Gaussian uncorrelated energetic disorder. Field and temperature dependences of drift mobility on the nonequilibrium transport regime relating to the time-of-flight experiment are in good agreement with the Monte-Carlo simulation results in a broad range of fields and temperatures using the same set of model parameters for both transport regimes.

Added: Feb 2, 2019
Article
Kolesnikov A., Budkov Y., Mollmer J. et al. The Journal of Physical Chemistry C. 2019. Vol. 123. No. 16. P. 10333-10338.

In this manuscript, we study the electrically induced breathing of Metal-Organic Framework (MOF) within a 2D lattice model. The Helmholtz free energy of the MOF in electric eld consists of two parts: the electrostatic energy of the dielectric body in the external electric eld and elastic energy of the framework. The rst contribution is calculated from the rst principles of statistical mechanics with an account of MOF symmetry. By minimizing the obtained free energy and solving the resulting system of equations, we obtain the local electric eld and the parameter of the unit cell (angle ). The paper also studies the cross-section area of the unit cell and the polarization as functions of the external electric eld. We obtain the hysteresis in the region of the structural transition of the framework. Our results are in qualitative agreement with the literature data of the molecular dynamics (MD) simulation of MIL-53(Cr).

Added: Apr 1, 2019
Article
Loganathan N., Yazaydin A. O., Bowers G. M. et al. The Journal of Physical Chemistry C. 2017. Vol. 121. No. 44. P. 24527-24540.

Grand Canonical Molecular Dynamics (GCMD) simulations were performed to investigate the intercalation of CO2 and H2O molecules in the interlayers of the smectite clay, Na-hectorite, at temperatures and pressures relevant to petroleum reservoir and geological carbon sequestration conditions and in equilibrium with H2O-saturated CO2. The computed adsorption isotherms indicate that CO2 molecules enter the interlayer space of Na-hectorite only when it is hydrated with approximately three H2O molecules per unit cell. The computed immersion energies show that the bilayer hydrate structure (2WL) contains less CO2 than the monolayer structure (1WL) but that the 2WL hydrate is the most thermodynamically stable state, consistent with experimental results for a similar Na-montmorillonite smectite. Under all T and P conditions examined (323–368 K and 90–150 bar), the CO2 molecules are adsorbed at the midplane of clay interlayers for the 1WL structure and closer to one of the basal surfaces for the 2WL structure. Interlayer CO2 molecules are dynamically less restricted in the 2WL structures. The CO2 molecules are preferentially located near basal surface oxygen atoms and H2O molecules rather than in coordination with Na+ ions. Accounting for the orientation and flexibility of the structural −OH groups of the clay layer has a significant effect on the details of the computed structure and dynamics of H2O and CO2 molecules but does not affect the overall trends with changing basal spacing or the principal structural and dynamical conclusions. Temperature and pressure in the ranges examined have little effect on the principal structural and energetic conclusions, but the rates of dynamical processes increase with increasing temperature, as expected.

Added: Nov 11, 2017
Article
Loganathan N., Kalinichev A. G. The Journal of Physical Chemistry C. 2017. Vol. 121. P. 7829-7836.

Adsorption and mobility of radioactive Cs+ isotopes in soil are among the most important factors affecting the long-term environmental footprint of nuclear accidents such as Chernobyl (1986) and Fukushima Daiichi (2011). In particular, Cs+ ions can be retained through their exchange with K+ naturally present in muscovite mica, one of the common soil mineral components. The ClayFF force field allowed us to realistically represent local inhomogeneities of the structure, composition, and charge on the muscovite (001) surface and to identify three structurally different types of adsorption sites. We performed molecular dynamics simulations of Cs+ and K+ adsorption at the hydrated muscovite surface and used quasi-one-dimensional site-specific potential of mean force calculations to quantify the energetics of ion exchange in this system for each individual site and for the entire muscovite surface on average. Irrespective of the type of adsorption site, both K+ and Cs+ cations are preferably adsorbed on the basal (001) muscovite surface at the centers of ditrigonal cavities as inner sphere surface complexes. The free energy difference between the most favorable and the least favorable surface sites for Cs+/K+ ion exchange amounts to 11.7 kJ/mol, with the most favorable sites occupying half of the surface and the least favorable type  - 1/6 of the surface and the rest exhibiting an intermediate adsorption and ion exchange capacity. The simulation results are compared with available thermodynamic estimates based on recent X-ray reflectivity measurements.

Added: Apr 30, 2017
Article
B.V. Andryushechkin, V.M. Shevlyuga (Шевлюга В. М., T.V. Pavlova et al. The Journal of Physical Chemistry C. 2018. Vol. 122. No. 50. P. 28862-28867.

Coadsorption of chlorine and oxygen on the Ag(111) surface has been studied with low-temperature scanning tunneling microscopy in combination with density functional theory calculations. Room-temperature adsorption of chlorine onto the Ag(111)-p(4 × 4)–O surface leads to the appearance of new bright objects located between protrusions of the 4 × 4 reconstruction. As chlorine adsorbs, objects form “rosettes” around corner holes. This configuration coincides with the configuration of the chlorine atoms in the Ag(111)-(3 × 3)–Cl reconstruction structure. We conclude that the adsorption of chlorine on the Ag(111)-p(4 × 4)–O surface occurs dissociatively, with chlorine atoms displacing oxygen atoms from the 4-fold positions. Adsorption of chlorine at 77 K results in the formation of the mixed Cl–O species on the Ag6 triangles of the p(4 × 4) reconstruction. Both scenarios of chlorine adsorption are unexpected and cannot be explained within a commonly accepted Ag6 model of the p(4 × 4) reconstruction.

Added: Jan 10, 2019
Article
Ngouana-Wakou B. F., Kalinichev A. G. The Journal of Physical Chemistry C. 2014. Vol. 118. P. 12758-12773.

Three new structural models of montmorillonite with differently distributed Al/Si and Mg/Al substitutions in the tetrahedral and octahedral clay layers are systematically developed and studied by means of MD simulations to quantify the possible effects of such substitutional disorder on the swelling behavior, the interlayer structure, and mobility of aqueous species. A very wide range of water content, from 0 to 700 mgwater/gclay is explored to derive the swelling properties of Cs-montmorillonite. The determined layer spacing does not differ much depending on the clay model. However, at low water contents up to 1-layer hydrate (~100 (mg water)/(g clay)) the variation of specific locations of the tetrahedral and octahedral substitutions in the two TOT clay layers slightly but noticeably affects the total hydration energy of the system. Using atom?atom radial distribution functions and the respective atomic coordination numbers we have identified for the three clay models not only the previously observed binding sites for Cs+ on the clay surface but also new ones that are correlated with the position of tetrahedral substitution in the structure. The mobility of Cs+ ions and H2O diffusion coefficients, as expected, gradually increase both with increasing water content and with increasing distance from the clay surface, but they still remain 2 to 4 times lower than the corresponding bulk values. Only small differences were observed between the three Cs-montmorillonite models, but these differences are predicted to increase in the case of higher charge density of the clay layers and/or interlayer cations.

Added: Apr 30, 2017
Article
Loganathan N., Yazaydin A. O., Bowers G. M. et al. The Journal of Physical Chemistry C. 2016. Vol. 120. P. 10298-10310.

Classical molecular dynamics simulations were performed for the smectite clay hectorite with charge-balancing Cs+ cations using a newly developed structural model with a disordered distribution of Li/Mg substitutions in the octahedral sheet and the fully flexible ClayFF force field. Calculations for systems with interlayer galleries containing 0 to 19 H2O/Cs+ suggest that the monolayer hydrate is the only stable state at all relative humidities at ambient pressure and temperature, in agreement with experimental results and previous molecular calculations. The basal spacing of this structure is also in good agreement with experimental values. In contrast to previous molecular modeling results, however, the new simulations show that interlayer Cs+ occurs on 2 different inner sphere adsorption sites: above the center of ditrigonal cavities and above Si tetrahedra. Unlike previous simulations, which employed a rigid clay model and fixed orientations of the structural −OH groups, the present results are obtained for an unconstrained clay substrate structure, where the structural −OH groups are able to assume various orientations, including being nearly parallel to the clay layers. This flexibility allows the Cs+ ions to approach the surface more closely above the centers of the hexagonal rings. In this structural arrangement, Cs+ ions are not hydrated by the H2O molecules which share the same interlayer plane, but rather by the H2O molecules coordinated to the opposite surface. In contrast, on the external basal surface, a significant fraction of H2O molecules are adsorbed above the centers of ditrigonal cavities adjacent to adsorbed Cs+ ions. For these H2O molecules, both HH2O atoms coordinate and H-bond to Ob surface oxygen atoms. The mean residence times for the Cs+ - H2O, Cs+ - Ob, and H2O - Ob coordination pairs show that Cs+ ions are more strongly coordinated with Ob atoms than H2O molecules. This result is the opposite of the behavior in Ca-hectorite, due to the much smaller hydration energy of Cs+ compared to that of Ca(2+).

Added: Apr 30, 2017
Article
Morrow C. P., Yazaydin A. O., Krishnan M. et al. The Journal of Physical Chemistry C. 2013. Vol. 117. P. 5172--5187.

This paper presents a classical molecular dynamics (MD) and metadynamics investigation of the relationships between the structure, energetics, and dynamics of Na-hydroxyhectorite and serves to provide additional, molecular-scale insight into the interlayer hydration of this mineral. The computational results support a model for interlayer H2O structure and dynamics based on 2H NMR spectroscopy and indicate that H2O molecules undergo simultaneous fast librational motions about the H2O C2 symmetry axis and site hopping with C3 symmetry with respect to the surface normal. Hydration energy minima occur at one-, one-and-one-half-, and two-water-layer hydrates, which for the composition modeled correspond to 3, 5.5, and 10 H2O/Na+, respectively. Na+ ions are coordinated by basal O atoms (OMIN) at the lowest hydration levels and by H2O molecules (OH2O) in the two-layer hydrate, and H2O molecules have an average of three H-bonds at the greatest hydration levels. The metadynamics calculations yield activation energies for site hopping of H2O molecules of ~6.0 kJ/mol for the one-layer structure and ~3.3 kJ/mol for hopping between layers in the two-layer structure. Computed diffusion coefficients for water and Na+ are substantially less than in bulk liquid water, as expected in a nanoconfined environment, and are in good agreement with previous results.

Added: Apr 30, 2017
Article
Pouvreau M., Greathouse J. A., Cygan R. T. et al. The Journal of Physical Chemistry C. 2017. Vol. 121. No. 27. P. 14757-14771.

Molecular scale understanding of the structure and properties of aqueous interfaces with clays, metal (oxy-) hydroxides, layered double hydroxides, and other inorganic phases is strongly affected by significant degrees of structural and compositional disorder of the interfaces. ClayFF was originally developed as a robust and flexible force field for classical molecular simulations of such systems (Cygan, R. T.; Liang, J.-J.; Kalinichev, A. G. J. Phys. Chem. B 2004, 108, 1255-1266). However, despite its success, multiple limitations have also become evident with its use. One of the most important limitations is the difficulty to accurately model the edges of finite size nanoparticles or pores rather than infinitely layered periodic structures. Here we propose a systematic approach to solve this problem by developing specific metal-O-H (M-O-H) bending terms for ClayFF, Ebend = k (theta - theta0)**2 to better describe the structure and dynamics of singly protonated hydroxyl groups at mineral surfaces, particularly edge surfaces. On the basis of a series of DFT calculations, the optimal values of the Al-O-H and Mg-O-H parameters for Al and Mg in octahedral coordination are determined to be theta0(AlOH) = theta0(MgOH) = 110°, k(AlOH) = 15 kcal mol(-1) rad(-2) and k(MgOH) = 6 kcal mol(-1) rad(-2). Molecular dynamics simulations were performed for fully hydrated models of the basal and edge surfaces of gibbsite, Al(OH)3, and brucite, Mg(OH)2, at the DFT level of theory and at the classical level, using ClayFF with and without the M-O-H term. The addition of the new bending term leads to a much more accurate representation of the orientation of O-H groups at the basal and edge surfaces. The previously observed unrealistic desorption of OH2 groups from the particle edges within the original ClayFF model is also strongly constrained by the new modification.

Added: Jul 13, 2017
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