Cubic zirconium tungstate (α-ZrW2O8), a notorious negative thermal expansion (NTE) material, has been investigated within the framework of density functional perturbation theory (DFPT), combined with experimental characterization to assess and validate computational results. Spectroscopic, mechanical and thermodynamic properties have been derived from DFPT calculations. A systematic comparison of DFPT-simulated infrared, Raman, and phonon density-of-state spectra with Fourier transform far-/mid-infrared and Raman data collected in this study, as well as with available inelastic neutron scattering measurements, shows the supe-rior accuracy of the PBEsol exchange-correlation functional over standard PBE calculations. The thermal evolution of the Grüneisen parameter computed within the quasi-harmonic approximation exhibits negative values below the Debye temperature, consistent with the observed NTE characteristics of α-ZrW2O8. The standard molar heat capacity is predicted to be C$0\atop{P}$=193.8 and 192.2 J.mol-1.K-1 with PBE and PBEsol, respectively, ca. 7% lower than calorimetric data. In conclusion, these results demonstrate the accuracy of the DFPT/PBEsol approach for studying the spectroscopic, mechanical and thermodynamic properties of materials with anomalous thermal expansion.
Our team has investigated a series of soluble coordination complexes for use as tags to monitor underground fluid flows in reservoirs. While most of the metal-ligand (M-L) complexes were based on the dianionic salen family of ligands, conceptually other ligands such as porphyrins or phthalocyanines could be used with similar success. Detection and identification of these species in solution were performed by inductively coupled plasma (ICP) or Raman/resonance Raman (rR) spectroscopy. The preparation of a large number of new M-L salen complexes was accomplished. Complexes were prepared that were soluble in either water or hydrocarbons to allow for flexibility in use. Unambiguous identification of these complexes allowed for meaningful molecular dynamics (MD) calculations to be performed, so that the attraction of the M-L complexes to either the rock formation or the liquid media could be evaluated. The use of soluble M-L species was found to avoid issues of rock deposition.
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 (θ - θ0)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 θ0,AlOH = θ0,MgOH = 110°, kAlOH = 15 kcal mol-1 rad-2 and kMgOH = 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.
Here, first-principles molecular dynamics simulations were used to investigate the dissociation of sarin (GB) on the calcium silicate hydrate (CSH) mineral tobermorite (TBM), a surrogate for cement. CSH minerals (including TBM) and amorphous materials of similar composition are the major components of Portland cement, the binding agent of concrete. Metadynamics simulations were used to investigate the effect of the TBM surface and confinement in a microscale pore on the mechanism and free energy of dissociation of GB. Our results indicate that both the adsorption site and the humidity of the local environment significantly affect the sarin dissociation energy. In particular, sarin dissociation in a low-water environment occurs via a dealkylation mechanism, which is consistent with previous experimental studies.
In this study, oxygen selectivity in metal-organic frameworks (MOFs) at exceptionally high temperatures originally predicted by Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) modeling is now confirmed by synthesis, sorption metal center access, in particular Sc and Fe. Based on DFT M-O2 binding energies, we chose the large pored MIL-100 framework for metal center access, in particular Sc and Fe. Both resulted in preferential O2 and N2 gas uptake at temperatures ranging from 77 K to ambient temperatures (258 K, 298 K and 313 K).
The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O2 and N2 in the M2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.