Johannes Diderik van der Waals

Johannes Diderik van der Waals (joːˈɦɑnəz ˈdidərɪk fɑn dər ˈʋaːls; 23 November 1837 – 8 March 1923) was a Dutch theoretical physicist and thermodynamicist famous for his pioneering work on the equation of state for gases and liquids. Van der Waals started his career as a schoolteacher. He became the first physics professor of the University of Amsterdam when in 1877 the old Athenaeum was upgraded to Municipal University. Van der Waals won the 1910 Nobel Prize in physics for his work on the equation of state for gases and liquids. His name is primarily associated with the Van der Waals equation of state that describes the behavior of gases and their condensation to the liquid phase. His name is also associated with Van der Waals forces (forces between stable molecules), with Van der Waals molecules (small molecular clusters bound by Van der Waals forces), and with Van der Waals radii (sizes of molecules). As James Clerk Maxwell said, "there can be no doubt that the name of Van der Waal

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On the non-analytic behaviour of thermodynamic potentials at first order phase transitions

Sacha Friedli

This work is devoted to the study of the analyticity properties of thermodynamic potentials (free energy, pressure) for classical lattice systems at low temperature. The central topic of our analysis, in this framework, is to show rigorously the absence of analytic continuation at points of first order phase transition. Our first result applies to the general class of two phase models considered in the Theory of Pirogov-Sinai. The analysis reveals that the Peirls condition, which is the basic hypothesis of the theory, suffices to show the absence of analytic continuation of the pressure at the transition point. In a second part, we study a particular two body potential, of the form γdJ(γx), where γ > 0 is a small parameter and J a function with bounded support (in the limit γ —> 0, this potential gives a rigorous justification of the "equal area rule" of the van der Waals-Maxwell Theory). For all small strictly positive values of the parameter γ, we show that the free energy has no analytic continuation at the transition points. These results confirm early conjectures stating that the finiteness of the range of interaction is responsible for the presence of singularities in the thermodynamic potentials.

EPFL2003

Performance of optimized atom-centered potentials for weakly bonded systems using density functional theory

Ursula Röthlisberger, Ivano Tavernelli, Anatole von Lilienfeld

Recently, we have introduced a scheme for optimizing atom-based nonlocal external potentials within the framework of d. functional theory (DFT) in order to systematically improve the description of mol. properties [Phys. Rev. Lett. 93, 153004 (2004); J. Chem. Phys. 122, 014113 (2005)]. In this study, we investigate a small library of dispersion-cor. atom-centered potentials (DCACP's) for C, Ar, Kr, and Br. To this end, we calibrate DCACP's in order to reproduce the equil. distance and binding energy of MP2 potential energy surfaces of the weakly bonded homodimers Ar2, Kr2, and (Br2)2. In all cases studied, using DFT with the generalized gradient approxn. functional BLYP and the DCACP's, the influence of dispersion forces on equil. and transition-state geometries, interaction energies, and transition barriers can be reproduced in good agreement with MP2 calcns. and without any significant increase in computational cost. The transferability of the DCACP's to other systems is assessed by addressing various weakly bonded complexes. We investigate (i) ideal van der Waals clusters of the type ArnKrm ( n,m={0,1,2,3,4} and 2?n+m?4), (ii) the effect of DCACP's on covalent bonds and conformers of the hydrocarbon mol. cyclooctatetraene which features a system of p bonds, and (iii) the competition of simultaneous electrostatic and dispersion forces for the equil. structure and transition states of the hydrogen bromide dimer (HBr)2. In all cases, the performance of the DCACP's to these extended set of systems is remarkably good. [on SciFinder (R)]

2005

Local stiffness and work function variations of hexagonal boron nitride on Cu(111)

Abhishek Grewal, Klaus Kern, Markus Ternes

Combined scanning tunnelling and atomic force microscopy using a qPlus sensor enables the measurement of electronic and mechanic properties of two-dimensional materials at the nanoscale. In this work, we study hexagonal boron nitride (h-BN), an atomically thin 2D layer, that is van der Waals-coupled to a Cu(111) surface. The system is of interest as a decoupling layer for functional 2D heterostructures due to the preservation of the h-BN bandgap and as a template for atomic and molecular adsorbates owing to its local electronic trapping potential due to the in-plane electric field. We obtain work function (Phi) variations on the h-BN/Cu(111) superstructure of the order of 100 meV using two independent methods, namely the shift of field emission resonances and the contact potential difference measured by Kelvin probe force microscopy. Using 3D force profiles of the same area we determine the relative stiffness of the Moire region allowing us to analyse both electronic and mechanical properties of the 2D layer simultaneously. We obtain a sheet stiffness of 9.4 +/- 0.9 N.m(-1), which is one order of magnitude higher than the one obtained for h-BN/Rh(111). Using constant force maps we are able to derive height profiles of h-BN/Cu(111) showing that the system has a corrugation of 0.6 +/- 0.2 angstrom, which helps to demystify the discussion around the flatness of the h-BN/Cu(111) substrate.

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