Showing papers by "Roberto Car published in 2013"
TL;DR: There is room for improvement in the description of water at ambient and high pressures remains and it is suggested that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.
Abstract: Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [B. Santra, J. Klimes, D. Alfe, A. Tkatchenko, B. Slater, A. Michaelides, R. Car, and M. Scheffler, Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive properties of the various phases, causing certain phases to be absent from the phase diagram. Therefore, room for improvement in the description of water at ambient and high pressures remains and we suggest that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.
134 citations
TL;DR: It is shown that WT-MetaD can be used to study the finite-size scaling behaviour of the free energy barrier separating the two liquids for systems containing 192, 300 and 400 ST2 molecules, and that larger systems must be examined to provide conclusive evidence of a first-order phase transition and associated second critical point.
Abstract: We investigate the metastable phase behaviour of the ST2 water model under deeply supercooled conditions. The phase behaviour is examined using umbrella sampling (US) and well-tempered metadynamics (WT-MetaD) simulations to compute the reversible free energy surface parameterized by density and bond-orientation order. We find that free energy surfaces computed with both techniques clearly show two liquid phases in coexistence, in agreement with our earlier US and grand canonical Monte Carlo calculations [Y. Liu, J. C. Palmer, A. Z. Panagiotopoulos and P. G. Debenedetti, J Chem Phys, 2012, 137, 214505; Y. Liu, A. Z. Panagiotopoulos and P. G. Debenedetti, J Chem Phys, 2009, 131, 104508]. While we demonstrate that US and WT-MetaD produce consistent results, the latter technique is estimated to be more computationally efficient by an order of magnitude. As a result, we show that WT-MetaD can be used to study the finite-size scaling behaviour of the free energy barrier separating the two liquids for systems containing 192, 300 and 400 ST2 molecules. Although our results are consistent with the expected N2/3 scaling law, we conclude that larger systems must be examined to provide conclusive evidence of a first-order phase transition and associated second critical point.
99 citations
TL;DR: In this paper, the problem of finding the optimal set of shortest-range pair interactions within a family of Hamiltonians whose corresponding ground state is a targeted spin configuration such that the difference in energies between the energetically closest competitor and the target is maximized is solved exactly using linear programming.
Abstract: In this work, we extend recent inverse statistical-mechanical methods developed for many-particle systems to the case of spin systems. For simplicity, we focus in this initial study on the two-state Ising model with radial spin-spin interactions of finite range (i.e., extending beyond nearest-neighbor sites) on the square lattice under periodic boundary conditions. Our interest herein is to find the optimal set of shortest-range pair interactions within this family of Hamiltonians, whose corresponding ground state is a targeted spin configuration such that the difference in energies between the energetically closest competitor and the target is maximized. For an exhaustive list of competitors, this optimization problem is solved exactly using linear programming. The possible outcomes for a given target configuration can be organized into the following three solution classes: unique (nondegenerate) ground state (class I), degenerate ground states (class II), and solutions not contained in the previous two classes (class III). We have chosen to study a general family of striped-phase spin configurations comprised of alternating parallel bands of up and down spins of varying thicknesses and a general family of rectangular block checkerboard spin configurations with variable block size, which is a generalization of the classic antiferromagnetic Ising model. Our findings demonstrate that the structurally anisotropic striped phases, in which the thicknesses of up- and down-spin bands are equal, are unique ground states for isotropic short-ranged interactions. By contrast, virtually all of the block checkerboard targets are either degenerate or fall within class III solutions. The degenerate class II spin configurations are identified up to a certain block size. We also consider other target spin configurations with different degrees of global symmetries and order. Our investigation reveals that the solution class to which a target belongs depends sensitively on the nature of the target radial spin-spin correlation function. In the future, it will be interesting to explore whether such inverse statistical-mechanical techniques could be employed to design materials with desired spin properties.
22 citations
TL;DR: Demonstration by ab initio simulations that the [FeFe]P/FeS2 catalyst/electrode complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently.
Abstract: Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 104/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe]P/FeS2, a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe]P/FeS2 is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant.
7 citations
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TL;DR: In this paper, a novel energy functional for ground-state electronic-structure calculations is proposed. The functional derives from a sequence of controlled approximations to the two-particle density matrix.
Abstract: We introduce a novel energy functional for ground-state electronic-structure calculations. Its fundamental variables are the natural spin-orbitals of the implied singlet many-body wave function and their joint occupation probabilities. The functional derives from a sequence of controlled approximations to the two-particle density matrix. Algebraic scaling of computational cost with electron number is obtainable in general, and Hartree-Fock scaling in the seniority-zero version of the theory. Results obtained with the latter version for saturated small molecular systems are compared with those of highly-accurate quantum-chemical computations. The numerical results are variational, capturing most of the correlation energy from equilibrium to dissociation. Their accuracy is considerably greater than that obtainable with current density-functional theory approximations and with current functionals of the one-particle density matrix only.