The vibrational spectra of natural and perdeuterated monochlorogallane, H2Ga([mu]-Cl)2GaH2, and an empirical harmonic potential function

The infrared and Raman spectra of monochlorogallane and its fully deuterated isotopomer are recorded and assigned on the basis of the dimeric structures. H2Ga(μ-Cl)2GaH2 and D2Ga(μ-Cl)2GaD2, conforming to D2 symmetry. The observed frequencies are corrected for anharmonicity and fitted to a potential function in which 19 of the 33 independent force constants are refined.

Ferric and ferrous iron in nitroso-myoglobin: computer simulations of stable and metastable states and their infrared spectra

The binding of NO to iron is involved in the biological function of many heme proteins. Contrary to ligands like CO and O-2, which only bind to ferrous (Fe-II) iron, NO binds to both ferrous and ferric (Fe-II) iron. In a particular protein, the natural oxidation state can therefore be expected to be tailored to the required function. Herein, we present an ob initio potential-energy surface for ferric iron interacting with NO. This potential-energy surface exhibits three minima corresponding to eta'-NO coordination (the global minimum), eta(1)-ON coordination and eta(2) coordination. This contrasts with the potential-energy surface for Fe-II-NO, which ex- hibits only two minima (the eta(2) coordination mode for Fe-II is a transition state, not a minimum). In addition, the binding energies of NO are substantially larger for Fe-III than for Fe-II. We have performed molecular dynamics simulations for NO bound to ferric myoglobin (Mb(III)) and compare these with results obtained for Mb(II). Over the duration of our simulations (1.5 ns), all three binding modes are found to be stable at 200 K and transiently stable at 300 K, with eventual transformation to the eta(1)-NO global-minimum conformation. We discuss the implication of these results related to studies of rebinding processes in myoglobin.

Comments on some recent measurements of anomalously steep N2O and O3tracer spectra in the stratospheric surf zone

Recent aircraft measurements, primarily in the extratropics, of the horizontal variance of nitrous oxide (N2O) and ozone (O3) in the middle stratosphere indicate that horizontal spectra of the tracer variance scale nearly as k−2, where k is the spatial wavenumber along the aircraft flight track [Strahan and Mahlman, 1994; Bacmeister et al., 1996]. This spectral scaling has been regarded as inconsistent with the accepted picture of stratospheric tracer motion; large-scale quasi-two-dimensional tracer advection typically yields a k−1 scaling (i.e., the classical Batchelor spectrum). In this paper it is argued that the nearly k−2 scaling seen in the measurements is a natural outcome of quasi-two-dimensional filamentation of the polar vortex edge. The accepted picture of stratospheric tracer motion can thus be retained: no additional physical processes are needed to account for deviations from the Batchelor spectrum. Our argument is based on the finite lifetime of tracer filaments and on the “singularity spectrum” associated with a one-dimensional field composed of randomly spaced jumps in concentration.