Nonmonotonic dependence of the absolute entropy on temperature in supercooled Stillinger-Weber silicon

Using a recently developed thermodynamic integration method, we compute the precise values of the excess Gibbs free energy (G^e) of the high density liquid (HDL) phase with respect to the crystalline phase at different temperatures (T) in the supercooled region of the Stillinger-Weber (SW) silicon [F. H. Stillinger and T. A. Weber, Phys. Rev. B. 32, 5262 (1985)]. Based on the slope of G^e with respect to T, we find that the absolute entropy of the HDL phase increases as its enthalpy changes from the equilibrium value at T \ge 1065 K to the value corresponding to a non-equilibrium state at 1060 K. We find that the volume distribution in the equilibrium HDL phases become progressively broader as the temperature is reduced to 1060 K, exhibiting van-der-Waals (VDW) loop in the pressure-volume curves. Our results provides insight into the thermodynamic cause of the transition from the HDL phase to the low density phases in SW silicon, observed in earlier studies near 1060 K at zero pressure.Comment: This version is accepted for publication in Journal of Statistical Physics (11 figures, 1 table

Unraveling the performance of dispersion-corrected functionals for the accurate description of weakly bound natural polyphenols

Long-range non-covalent interactions play a key role in the chemistry of natural polyphenols. We have previously proposed a description of supramolecular polyphenol complexes by the B3P86 density functional coupled with some corrections for dispersion. We couple here the B3P86 functional with the D3 correction for dispersion, assessing systematically the accuracy of the new B3P86-D3 model using for that the well-known S66, HB23, NCCE31, and S12L datasets for non-covalent interactions. Furthermore, the association energies of these complexes were carefully compared to those obtained by other dispersion-corrected functionals, such as B(3)LYP-D3, BP86-D3 or B3P86-NL. Finally, this set of models were also applied to a database composed of seven non-covalent polyphenol complexes of the most interest.FDM acknowledges financial support from the Swedish Research Council (Grant No. 621-2014-4646) and SNIC (Swedish National Infrastructure for Computing) for providing computer resources. The work in Limoges (IB and PT) is supported by the “Conseil Régional du Limousin”. PT gratefully acknowledges the support by the Operational Program Research and Development Fund (project CZ.1.05/2.1.00/03.0058 of the Ministry of Education, Youth and Sports of the Czech Republic). IB gratefully acknowledges financial support from “Association Djerbienne en France”

Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections

In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.Financial support by the “Ministerio de Economía y Competitividad” (MINECO) of Spain and European FEDER funds through projects CTQ2011-27253 and CTQ2012-31914 is acknowledged. The support of the Generalitat Valenciana (Prometeo/2012/053) is also acknowledged. J.A. thanks the EU for the FP7-PEOPLE-2012-IEF-329513 grant. J.C. acknowledges the “Ministerio de Educación, Cultura y Deporte” (MECD) of Spain for a predoctoral FPU grant

Open-Shell First-Row Transition-Metal Polyhydride Complexes Based on the <i>fac</i>-[RuH₃(PR₃)₃]^- Building Block

High‐spin hydrides : A new class of stable paramagnetic polyhydride complexes [M{Ru(μ‐H)3(PTol3)3}2] (M=Cr–Ni) with an unprecedented trinuclear arrangement has been synthesized. The high‐spin central 3d metal ion is sandwiched between six hydride ligands in a distorted octahedral fashion

Unveiling the Surface Structure of Amorphous Solid Water via Selective Infrared Irradiation of OH Stretching Modes

In the quest to understand the formation of the building blocks of life, amorphous solid water (ASW) is one of the most widely studied molecular systems. Indeed, ASW is ubiquitous in the cold interstellar medium (ISM), where ASW-coated dust grains provide a catalytic surface for solid phase chemistry, and is believed to be present in the Earth’s atmosphere at high altitudes. It has been shown that the ice surface adsorbs small molecules such as CO, N2, or CH4, most likely at OH groups dangling from the surface. Our study presents completely new insights concerning the behavior of ASW upon selective infrared (IR) irradiation of its dangling modes. When irradiated, these surface H2O molecules reorganize, predominantly forming a stabilized monomer-like water mode on the ice surface. We show that we systematically provoke “hole-burning” effects (or net loss of oscillators) at the wavelength of irradiation and reproduce the same absorbed water monomer on the ASW surface. Our study suggests that all dangling modes share one common channel of vibrational relaxation; the ice remains amorphous but with a reduced range of binding sites, and thus an altered catalytic capacity

IR Selective Irradiations of Amorphous Solid Water Dangling Modes: Irradiation vs Annealing Effects

Amorphous solid water (ASW) is one of the most widely studied molecular systems. Ubiquitous in the interstellar medium (ISM) and potentially present in the upper layers of the Earth’s atmosphere, ASW plays a major role in heterogeneous physical chemistry. Small molecules form or accrete at the ice surface, bonding to water molecules with an OH bond projecting from the surface, so-called “dangling bonds”. These dangling OH are of crucial importance in the quest to identify and quantify surface reactions. Water ices in the ISM or Earth’s atmosphere undergo constant processing by thermal and irradiation effects, which can significantly affect both the bulk and surface structures and therefore the catalytic properties of the surface. In this work we have studied thermal and irradiation processing of ASW and determine that there is a photochemical processing pathway of the ice surface which is clearly distinct from purely thermal effects. Selective IR irradiations of each of the surface water modes led to the observation of a “hole-burning” at the irradiation frequency, counterbalanced by the production of a new band, identified as a water monomer interacting with the surface. The thermal effects, meanwhile, led to a global decrease of all the dangling modes due to global reorganization of the water ice structure. It is thus obvious that, depending on the processing history of an ice, its catalytic properties will not be affected in the same way. The fact that we observe an IR selective irradiation effect illustrates that some fraction of the vibrational energy, rather than being relaxed through the H-bonded network of the bulk ice, is trapped at the surface; this energy induces a reorganization of the surface structure, forming new trapping sites, and thus generating new catalytic properties