Torsional anharmonicity in the conformational thermodynamics of flexible molecules

We present an algorithm for calculating the conformational thermodynamics of large, flexible molecules that combines ab initio electronic structure theory calculations with a torsional path integral Monte Carlo (TPIMC) simulation. The new algorithm overcomes the previous limitations of the TPIMC method by including the thermodynamic contributions of non-torsional vibrational modes and by affordably incorporating the ab initio calculation of conformer electronic energies, and it improves the conventional ab initio treatment of conformational thermodynamics by accounting for the anharmonicity of the torsional modes. Using previously published ab initio results and new TPIMC calculations, we apply the algorithm to the conformers of the adrenaline molecule

Frequency shift of cesium clock transition due to blackbody radiation

We have performed ab initio calculations of the frequency shift induced by a static electric field on the cesium clock hyperfine transition. The calculations are used to find the frequency shifts due to blackbody radiation. Our result ($\delta \nu/E^2=-2.26(2)\times 10^{-10}$Hz/(V/m)$^2$) is in good agreement with early measurements and ab initio calculations performed in other groups. We present arguments against recent claims that the actual value of the effect might be smaller. The difference ($\sim$ 10%) between ab initio and semiempirical calculations is due to the contribution of the continuum spectrum to the sum over intermediate states.Comment: Accepted for publication in Phys. Rev. Let

Raman spectra of BN-nanotubes: Ab-initio and bond-polarizability model calculations

We present it ab-initio calculations of the non-resonant Raman spectra of zigzag and armchair BN nanotubes. In comparison, we implement a generalized bond-polarizability model where the parameters are extracted from first-principles calculations of the polarizability tensor of a BN sheet. For light-polarization along the tube-axis, the agreement between model and it ab-initio spectra is almost perfect. For perpendicular polarization, depolarization effects have to be included in the model in order to reproduce the it ab-initio Raman intensities.Comment: 4 pages, submitted to Phys. Rev. B rapid com

Ab initio Quantum and ab initio Molecular Dynamics of the Dissociative Adsorption of Hydrogen on Pd(100)

The dissociative adsorption of hydrogen on Pd(100) has been studied by ab initio quantum dynamics and ab initio molecular dynamics calculations. Treating all hydrogen degrees of freedom as dynamical coordinates implies a high dimensionality and requires statistical averages over thousands of trajectories. An efficient and accurate treatment of such extensive statistics is achieved in two steps: In a first step we evaluate the ab initio potential energy surface (PES) and determine an analytical representation. Then, in an independent second step dynamical calculations are performed on the analytical representation of the PES. Thus the dissociation dynamics is investigated without any crucial assumption except for the Born-Oppenheimer approximation which is anyhow employed when density-functional theory calculations are performed. The ab initio molecular dynamics is compared to detailed quantum dynamical calculations on exactly the same ab initio PES. The occurence of quantum oscillations in the sticking probability as a function of kinetic energy is addressed. They turn out to be very sensitive to the symmetry of the initial conditions. At low kinetic energies sticking is dominated by the steering effect which is illustrated using classical trajectories. The steering effects depends on the kinetic energy, but not on the mass of the molecules. Zero-point effects lead to strong differences between quantum and classical calculations of the sticking probability. The dependence of the sticking probability on the angle of incidence is analysed; it is found to be in good agreement with experimental data. The results show that the determination of the potential energy surface combined with high-dimensional dynamical calculations, in which all relevant degrees of freedon are taken into account, leads to a detailed understanding of the dissociation dynamics of hydrogen at a transition metal surface.Comment: 15 pages, 9 figures, subm. to Phys. Rev.

Short range correlations and the isospin dependence of nuclear correlation functions

Pair densities and associated correlation functions provide a critical tool for introducing many-body correlations into a wide-range of effective theories. Ab initio calculations show that two-nucleon pair-densities exhibit strong spin and isospin dependence. However, such calculations are not available for all nuclei of current interest. We therefore provide a simple model, which involves combining the short and long separation distance behavior using a single blending function, to accurately describe the two-nucleon correlations inherent in existing ab initio calculations. We show that the salient features of the correlation function arise from the features of the two-body short-range nuclear interaction, and that the suppression of the pp and nn pair-densities caused by the Pauli principle is important. Our procedure for obtaining pair-density functions and correlation functions can be applied to heavy nuclei which lack ab initio calculations.Comment: 5 pages, 4 figure

A comment on "Ab initio calculations of pressure-dependence of high-order elastic constants using finite deformations approach" by I. Mosyagin, A.V. Lugovskoy, O.M. Krasilnikov, Yu.Kh. Vekilov, S.I. Simak and I.A. Abrikosov

Recently, I. Mosyagin, A.V. Lugovskoy, O.M. Krasilnikov, Yu.Kh. Vekilov, S.I. Simak and I.A. Abrikosov in the paper: "Ab initio calculations of pressure-dependence of high-order elastic constants using finite deformations approach"[Computer Physics Communications 220 (2017) 2030] presented a description of a technique for ab initio calculations of the pressure dependence of second- and third-order elastic constants. Unfortunately, the work contains serious and fundamental flaws in the field of finite-deformation solid mechanics.Comment: 3 pages, 0 figure

Structural and electronic properties of silver/silicon interfaces and implications for solar cell performance

We present the results of an experimental and atomistic modelling investigation of the Sili- con/Silver (Si/Ag) interfaces found in industrial solar cells. We use small ab initio calculations to parameterize a new interatomic potential for the Si/Ag interaction. This interatomic potential is then validated against larger ab initio calculations as well as the results of previous experimental and theoretical studies of Si/Ag systems. The interatomic potential allows us to perform a large- scale search of the conformational space of Si/Ag interfaces identified from transmission electron microscopy (TEM) studies. The most favourable geometries thus identified are then used as the input for more accurate ab initio calculations. We demonstrate that the two interfaces which we identify experimentally have significantly different geometric and electronic structures. We also demonstrate how these different structures result in significantly different Schottky barriers at the interfaces