Clusters containing open-shell molecules. III. Quantum five-dimensional/two-surface bound-state calculations on ArnOH van der Waals clusters (X2Π, n=4 to 12)

This paper presents a theoretical study of the bound states of the open-shell OH radical in its ground electronic state(X2Π) interacting with n Ar atoms, for n from 4 to 12. After freezing the geometry of the Arn cage or subunit at the equilibrium structure (preceding paper), we carry out nonadiabatic five-dimensional quantum dynamics calculations on two coupled potential energy surfaces, using an extension of the method previously applied to closed-shell ArnHFclusters [J. Chem. Phys. 103, 1829 (1995)]. The method is based on a discrete variable representation (DVR) for the translational motion of OH relative to Arn, combined with a finite basis representation of the OH hindered rotation and electronic structure, including spin–orbit effects. The pattern of OH hindered rotor levels in clusters is similar to that in Ar–OH itself, though extended over three to four times the energy range for n=4 to 9. Ar12OH has a nearly spherical shell of Ar atoms around the OH, so the anisotropic splitting is very small. For n=10 and 11, the anisotropy may be viewed as arising from holes in an otherwise spherical shell, and the resulting patterns of hindered rotor levels are inverted versions of those for Ar2OH and Ar–OH

Instantons, supersymmetric vacua, and emergent geometries

We study instanton solutions and superpotentials for the large number of vacua of the plane-wave matrix model and a 2+1 dimensional Super Yang-Mills theory on $R\times S^2$ with sixteen supercharges. We get the superpotential in the weak coupling limit from the gauge theory description. We study the gravity description of these instantons. Perturbatively with respect to a background, they are Euclidean branes wrapping cycles in the dual gravity background. Moreover, the superpotential can be given by the energy of the electric charge system characterizing each vacuum. These charges are interpreted as the eigenvalues of matrices from a reduction for the 1/8 BPS sector of the gauge theories. We also discuss qualitatively the emergence of the extra spatial dimensions appeared on the gravity side.Comment: 29 pages, 3 figures, latex. v2: references added, comments added. v3: accepted version in PR

Near-dissociation states and coupled potential curves for the HeN+ complex

The near-dissociation microwave rovibronic spectra of HeN+ [Carrington et al., Chem. Phys. Lett. 262, 598 (1996)] are used to obtain coupled potential energy curves for the six electronic states correlating with He+N+ 3P0, 3P1, and 3P2. High-quality ab initio calculations are carried out, using a spin-restricted open-shell coupled-cluster method with an augmented correlation-consistent quintuple-zeta basis set (aug-cc-pV5Z). Fully coupled calculations of bound and quasibound states are performed, including all six electronic states, and suggest two possible assignments of the observed transitions. The potentials are then morphed (scaled) to reproduce the experimental frequencies. One of the two assignments, designated SH1, is preferred because it gives a more satisfactory explanation of the observed hyperfine splittings. The corresponding morphed potential has well depths of 1954 cm−1 and 192 cm−1 for the spin-free 3Σ− and 3Π curves, respectively

Expression of mitochondrial branched-chain aminotransferase and α-keto-acid dehydrogenase in rat brain: implications for neurotransmitter metabolism

In the brain, metabolism of the essential branched chain amino acids (BCAAs) leucine, isoleucine, and valine, is regulated in part by protein synthesis requirements. Excess BCAAs are catabolized or excreted. The first step in BCAA catabolism is catalyzed by the branched chain aminotransferase (BCAT) isozymes, mitochondrial BCATm and cytosolic BCATc. A product of this reaction, glutamate, is the major excitatory neurotransmitter and precursor of the major inhibitory neurotransmitter γ-aminobutyric acid (GABA). The BCATs are thought to participate in a α-keto-acid nitrogen shuttle that provides nitrogen for synthesis of glutamate from α-ketoglutarate. The branched-chain α-keto acid dehydrogenase enzyme complex (BCKDC) catalyzes the second, irreversible step in BCAA metabolism, which is oxidative decarboxylation of the branched-chain α-keto acid (BCKA) products of the BCAT reaction. Maple Syrup Urine Disease (MSUD) results from genetic defects in BCKDC, which leads to accumulation of toxic levels of BCAAs and BCKAs that result in brain swelling. Immunolocalization of BCATm and BCKDC in rats revealed that BCATm is present in astrocytes in white matter and in neuropil, while BCKDC is expressed only in neurons. BCATm appears uniformly distributed in astrocyte cell bodies throughout the brain. The segregation of BCATm to astrocytes and BCKDC to neurons provides further support for the existence of a BCAA-dependent glial-neuronal nitrogen shuttle since the data show that BCKAs produced by glial BCATm must be exported to neurons. Additionally, the neuronal localization of BCKDC suggests that MSUD is a neuronal defect involving insufficient oxidation of BCKAs, with secondary effects extending beyond the neuron

Reactions between cold methyl halide molecules and alkali-metal atoms

We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A→CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow

Large Effects of Electric Fields on Atom-Molecule Collisions at Millikelvin Temperatures

Controlling interactions between cold molecules using external fields can elucidate the role of quantum mechanics in molecular collisions. We create a new experimental platform in which ultracold rubidium atoms and cold ammonia molecules are separately trapped by magnetic and electric fields and then combined to study collisions. We observe inelastic processes that are faster than expected from earlier field-free calculations. We use quantum scattering calculations to show that electric fields can have a major effect on collision outcomes, even in the absence of dipole-dipole interactions.Comment: 5 pages, 4 figure