Potential energy surfaces for HenNe+ ions: ab initio and diatomics-in-molecule results

The potential energy surface of He2Ne+ has been reinvestigated using a combination of ab initio and diatomics-in-molecule (DIM) calculations. In contrast to the reports of two recent studies the ion is found to have an asymmetric linear He-Ne-He structure, with no barrier to formation from the separated atoms on the ground-state surface. The He-Ne+ bond lengths at the potential minimum are 1.51 and 1.81 A, and the total bonding energy is 0.717 eV. Comparing the He2Ne+ energy to that of HeNe+, the bonding energy for the second helium atom is 0.06 eV, about 10% of that of the first He atom. The saddle point between the two equivalent minima is a symmetric structure, 0.0074 eV above the potential minimum. A symmetric geometry becomes the overall potential minimum if the 2s hole on the Ne is excluded from the reference states of a multireference configuration interaction calculation. A DIM potential was created for the HenNe+ family of ions. The DIM potential is consistent with the asymmetric He2Ne+ ion serving as a core; it predicts a slightly more asymmetric geometry than the ab initio results. Additional helium atoms form five-membered rings around the bonds of the core ion to fill the first shell and then add to the ends of the cluster. The asymmetric core ion and the highly compact structure help to account for the lack of apparent shell structure in the mass spectrometry of HenNe+ clusters. Finally, we recommend that the value De=0.63+/-0.04 eV be adopted for the ground state of HeNe+.     

Time Window Expansion for HDX Analysis of an Intrinsically Disordered Protein

Application of typical HDX methods to examine intrinsically disordered proteins (IDP), proteins that are natively unstructured and highly dynamic at physiological pH, is limited because of the rapid exchange of unprotected amide hydrogens with solvent. The exchange rates of these fast exchanging amides are usually faster than the shortest time scale (10 s) employed in typical automated HDX-MS experiments. Considering the functional importance of IDPs and their association with many diseases, it is valuable to develop methods that allow the study of solution dynamics of these proteins as well as the ability to probe the interaction of IDPs with their wide range of binding partners. Here, we report the application of time window expansion to the millisecond range by altering the on-exchange pH of the HDX experiment to study a well-characterized IDP; the activation domain of the nuclear receptor coactivator, peroxisome proliferator-activated receptor gamma coactivator-1 alpha (PGC-1α). This method enabled mapping the regions of PGC-1α that are stabilized upon binding the ligand binding domain (LBD) of the nuclear receptor peroxisome proliferator-activated receptor gamma (PPARγ). We further demonstrate the method’s applicability to other binding partners of the IDP PGC-1α and pave the way for characterizing many other biologically important ID proteins.

Exchange monte carlo for molecular simulations with monoelectronic hamiltonians

We introduce a general Monte Carlo scheme for achieving atomistic simulations with monoelectronic Hamiltonians including the thermalization of both nuclear and electronic degrees of freedom. The kinetic Monte Carlo algorithm is used to obtain the exact occupation numbers of the electronic levels at canonical equilibrium, and comparison is made with Fermi-Dirac statistics in infinite and finite systems. The effects of a nonzero electronic temperature on the thermodynamic properties of liquid silver and sodium clusters are presented.     

Vibrations and thermodynamics of clusters of polycyclic aromatic hydrocarbon molecules: the role of internal modes

The vibrational spectra of clusters of coronene molecules are theoretically calculated using a mixed quantum/classical scheme, each molecule being described by a tight-binding Hamiltonian, the intermolecular forces being provided by explicit Lennard-Jones and point charge sites. The normal modes of vibrations are shown to exhibit significant variations upon clustering. In particular, for large clusters intra- and intermolecular modes tend to mix and fill the mid-infrared range. We also calculate the heat capacity of the (C24H12)8 cluster as a function of temperature, emphasizing the isomerizations that take place during melting. Quantum delocalization effects, as obtained from the Pitzer-Gwinn semiclassical approximation, are important enough to wash out all signatures of the structural transitions on the caloric curve. On the basis of a simple two-state model we estimate that clusters containing about 300 molecules are required for melting to be detected on the caloric curve.     

Self-consistent field tight-binding model for neutral and (multi-) charged carbon clusters

A semiempirical model for carbon clusters modeling is presented, along with structural and dynamical applications. The model is a tight-binding scheme with additional one- and two-center distance-dependent electrostatic interactions treated self-consistently. This approach, which explicitly accounts for charge relaxation, allows us to treat neutral and (multi-) charged clusters not only at equilibrium but also in dissociative regions. The equilibrium properties, geometries, harmonic spectra, and relative stabilities of the stable isomers of neutral and singly charged clusters in the range n=1-14, for C(20) and C(60), are found to reproduce the results of ab initio calculations. The model is also shown to be successful in describing the stability and fragmentation energies of dictations in the range n=2-10 and allows the determination of their Coulomb barriers, as examplified for the smallest sizes (C(2) (2+),C(3) (2+),C(4) (2+)). We also present time-dependent mean-field and linear response optical spectra for the C(8) and C(60) clusters and discuss their relevance with respect to existing calculations.     

A monopole mass filter with a hyperbolic V-shaped electrode

In this article we compare the classical monopole mass filter of von Zahn and the monopole mass filter with a hyperbolic V-shaped electrode. The experimental results and those of computer simulation for both mass spectrometers are presented. We show that the replacement of a conventional 90 degrees V-shaped electrode by an electrode with a hyperbolic profile substantially improves the peak shape of any given mass, and increases the mass resolution by a factor of 3-4 and the abundance sensitivity by a factor of 100. The potential of high analytical performance combined with electroforming techniques for electrode manufacture indicate future practical uses of such instruments. Copyright 1999 John Wiley & Sons, Ltd.     

A three body approach to study the structural properties of 2-n halo nuclei and the search for Efimov states

The discovery of neutron rich isotopes of the lightest elements on the neutron drip line exhibiting a halo structure has opened up new vistas in research activities. The novel structural features associated with the halo phenomena have been the subject for extensive theoretical and experimental investigations in recent times. In this talk, I propose to present a broad overview of the recent developments in this field, bringing out the striking features which show that a large number oflight nuclei near the neutron drip line are characterized by a clear separation between a ‘normal’ core nucleus and a loosely bound low density veil of neutrons. Specifically, the two neutron halos offer a natural premises, from a theoretical standpoint, to employ three body techniques for studying their detailed structural properties. A considerable part of the talk will be devoted to report and highlight the results on a number of light halo nuclei such as ¹¹Li, ¹¹Be, ¹⁹B and ²²C on which we have been carrying out investigations employing a simple but realistic three body model. These three body systems which have been termed as ‘Borromean’ (i.e while three body systems are bound, the corresponding binary subsystems on the other hand are unbound) are characterized by large spacial extension and very low separation energy of the neutron. They are, therefore, ideally suited for exploring the possibility of the existence of Efimov states in two neutron halo nuclei. We have recently carried out the three body analyses to predict the possibility of the occurrence of such states on which experimental work at various laboratories is underway.