Behaviour of ‘free-standing’ hollow Au nanocages at finite temperatures: a BOMD study

Finite-temperature behaviour of a hollow golden cage (HGC) plays a crucialrole in its potential applications as a catalyst, drug delivery agent, contrasting agent and so on. This physico-chemical property of HGCs is not well understood so far. In that context, Born–Oppenheimer molecular dynamics (BOMD) simulations are performed on a well-known ‘free-standing’ HGC. The cluster considered in this study is the ground state Au₁₈ cluster (a cage with a diameter of about >5.5 Å). The results thus obtained are compared with the BOMD simulation results reported earlier on Au₃₂ icosahedron cage, a conformation with a diameter of nearly. The sphericity of both the clusters is studied using a shape deformation parameter as a function of time and temperature. These results are supplemented by radial distribution function at various temperatures. The observations and analysis of results indicate that, both the clusters retain an HGC conformation from 300 to 400 K, admitting structural fluxionality by the Au₁₈ cluster. Remarkably, the Au₁₈ cluster is able to maintain its hollowness and sphericity up to a high temperature of 1000 K. Underlying structural and electronic properties influencing the individualistic behaviour of cages are highlighted. Composition of the frontier molecular orbitals and the charge distribution play a crucial role in the finite-temperature behaviour of the Au cages. The conclusions are supplemented by supporting calculations on another degenerate ground state Au₁₈ hollow cage and a well-known pyramidal Au₁₈ cage at 300 and 400 K.     

I.I. Rabi: The Two Cultures and the Universal Culture of Science

I set forth and discuss I.I. Rabis views on the nature of science and society, focusing specifically on Rabis views on science and government, science and education, and science and religion. I also explore the influence of Rabi and C.P. Snow on each other. In the 1960s, Rabi set forth his mature and boldest positions, advocating science as the center of education and science as the replacement for religion. His positions culminate in science as the universal culture. I highlight Rabi not only as a scientist and public servant, but also as a public intellectual actively engaged with and connected to major issues of his time.Michael A. Day is Professor of Physics at Lebanon Valley College. He holds doctorates in both physics and philosophy.     

A Conversation with Lee Alvin DuBridge - Part II

Physicist Lee A. DuBridge became president of the California Institute of Technology in 1946. In this interview he recalls his dealings at Caltech with Linus Pauling; his memories of George W. Beadle, Theodore von Kármán, and J. Robert Oppenheimer; the military Vista Project at Caltech; and the difficulties surrounding the deportation of Hsue-Shen Tsien, Caltech's Goddard Professor of Jet Propulsion.     

A Conversation with William A. Fowler – Part I

Nobel laureate William A. Fowler recalls his early education in physics; his part in the history of nuclear physics at the California Institute of Technology in the 1930s; parallel efforts elsewhere, particularly at Berkeley and the Department of Terrestrial Magnetism in Washington,D.C.; his contacts with J. Robert Oppenheimer; and his work with Charles C. Lauritsen and Tommy Lauritsen before and after World War II.John Greenberg received his Ph.D. degree from the University of Wisconsin and was Caltech research fellow in history from 1980–1984. The Editors were saddened to learn that he died while this interview was in press. Requests for reprints may be directed to Judith R. Goodstein, Institute Archives 015A-74, Caltech, Pasadena, CA 91125 USA; e-mail: jrg@caltech.edu.     

Nuclear dynamics in the vicinity of a crossing seam: Vibrational spectrum of HD2 revisited

So far, most studies of the geometric phase effect have presumed that the phase is path‐independent; hence, one must supply another restriction concerning the boundary condition on the nuclear wave functions when dealing with nonsymmetric isotopomers of X₃ systems. We report calculations of the vibrational spectra of HD₂ using a recently proposed generalized Born–Oppenheimer (GBO) formalism. The calculations demonstrate that there are significant differences between the results calculated from the present GBO method and those based on the preceding presumption. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 83: 279–285, 2001     

Molecular mechanism of the cesium and rubidium selective binding to the calix[4]arene revealed by Born–Oppenheimer molecular dynamics simulation and electron density analysis

1. Download : Download high-res image (192KB)
2. Download : Download full-size image

     

Nature of hydration shells of a polyoxy‐anion with a large cationic centre: The case of iodate ion in water

The structural nature of the solvation shells of an iodate ion, which is known to be a polyoxy‐anion with a large cationic centre, is investigated by means of Born–Oppenheimer molecular dynamics (BOMD) simulations using BLYP and the dispersion corrected BLYP‐D3 functionals. The iodate ion is found to have two distinct solvation regions around the positively charged iodine (iodine solvation shell or ISS) and the negatively charged oxygens (oxygen solvation shell or OSS). We have looked at the spatial, orientational, and hydrogen bond distributions of water in the two solvation regions. It is found that the water orientational profile in the ISS is typical of a cation hydration shell. The hydrogen bonded structure of water in the OSS is found to be very similar to that of the bulk water structure. Thus, the iodate ion essentially behaves like a positively charged iodine ion in water as if there is no anionic part. This explains why the cationic character of the iodate ion was prominently seen in earlier studies. The arrangement of water molecules in the two solvation shells and in the intervening regions around the iodate ion is further resolved by looking at structural cross‐correlations. The electronic properties of the solvation shells are also looked at by calculating the solute–solvent orbital overlap and dipole moments of the solute and solvation shell water. We have also performed BOMD simulations of iodate ion‐water clusters at experimentally relevant conditions. The simulation results are found to be in agreement with experimental results. © 2018 Wiley Periodicals, Inc.     

Hydration structure of Na+ and K+ from ab initio molecular dynamics based on modern density functional theory

Molecular dynamics (Born–Oppenheimer) simulations based on density functional theory have been carried out to investigate the solvation structure of monovalent Na⁺ and K⁺ cations in water under ambient conditions. Four recently proposed van der Waals (vdW) density functionals (LMKLL, DRSLL, DRSLL-PBE, DRSLL-optB88), the semiempirical vdW method of Grimme (BLYP-D3) and conventional gradient-corrected (GGA-BLYP) density functionals are applied in order to evaluate their accuracy in describing the hydration structure of alkali metal ions. Theoretical results are compared to available experimental data. Our results indicate that addition of corrections accounting for dispersion forces significantly improves the agreement between predicted and measured coordination numbers for both Na⁺ and K⁺ cations. Analysis of radial distribution functions brings further support to the notion that the choice of the generalised gradient approximation density functional impacts crucially on the computed structural properties. DRSLL-optB88 and BLYP-D3 provide the best agreement with experiment.     

Hermann Jahn and Rudolf Renner of the Jahn–Teller and Renner–Teller effects

Vibronic interactions have received increasing attention in modern structural chemistry. Edward Teller played a pioneering role in understanding and describing them during the “molecular physics” period of his scientific career. Very little is known about the two scientists who contributed significantly to our knowledge about these effects and whose names have become associated with Teller’s. This Editorial is devoted to Hermann Jahn and Rudolf Renner and attempts to lift them out of oblivion by paying them tribute for their contributions.