ALBERT

Notes: The IBr fragment rotational state distributions that result when the NeIBr van der Waals molecule undergoes vibrational predissociation have been measured in a pump–probe laser-induced fluorescence experiment. Independent of initial vibrational state and the number of quanta of vibrational energy lost from the I–Br coordinate, the rotational distributions extend over the full range of energetically accessible states. From the observation of energetic constraints on the rotational distribution, the dissociation energy (D0) is calculated to be 65.5±1.2 cm−1 for the A electronic state, v=16. For the X electronic state, v=0, D0=71.8±1.2 cm−1. Quantum mechanical bound state calculations carried out on a model A electronic state potential energy surface are in quantitative agreement with this result. The rotational distributions are broader than that predicted by either a Franck–Condon or classical impulsive model for the dissociation. The distributions are qualitatively in accord with classical trajectory calculations. Analysis of specific rotational distributions in the context of the energy gap law shows poor quantitative agreement. The average fragment rotational energy relative to analogous Ne-containing complexes is, however, qualitatively predicted by the energy gap relations.

Notes: The degree of vibrational excitation in the IBr fragment from the vibrational predissociation of NeIBr (A 3Π1) has been measured using two-color pump–probe laser-induced fluorescence spectroscopy. We find that for the lowest initial vibrational states examined, Δv=−1 dissociation pathways dominate the dynamics, while this channel is closed for v≥17. From this result, the A state binding energy (D0) of the complex is determined to be 67±4 cm−1, while that in the X electronic state is found to be 73±4 cm−1. The X state binding energy is identical to that for NeI2 and NeBr2, suggesting that the potential energy surface for NeIBr can be constructed from a summation of atom–atom pair potentials; we present such a model potential energy surface. The variations in the vibrational branching ratios, when combined with the trends in the predissociation rates, point to the importance of fragment rotational excitation in the dynamics of the dissociation.

Notes: The rotational, vibrational and fine-structure state distributions for the reaction 16O(1D)+ H218O →16OH +18OH, triggered by 266 nm photolysis of O3, have been measured under conditions where less than 1% of the nascent fragments experienced collisions prior to detection. The distributions are qualitatively different than those reported earlier for 266 nm photolysis, which were evidently affected by collisions. The rotational and vibrational state distributions are similar to recent 248 nm photolysis experiments, but with differences attributed to collisional and/or energetic effects in those experiments. The "new'' 16OH is formed with vibrational populations in the ratio 0.39(v=0):0.29(v=1):0.3(v≥2). Gaussian rotational energy distributions peaked near N=12 give average rotational energies of 〈Erot〉 = 3440 and 2780 cm−1 for 16OH v=0 and v=1, respectively. The "old'' 18OH is much colder with vibrational populations 0.94(v=0):0.06(v=1) and a 18OH v=0 Gaussian rotational energy distribution characterized by 〈Erot〉 = 1920 cm−1.There is negligible rotational alignment of the 16OH fragments [βμJ' = β20(02) = 5A(0)2/4 = 0.06± 0.09], which is significantly less than expected for fragment rotations aligned with respect to the O+H2O relative velocity vector. The spin-orbit propensities deviate slightly from the statistical expectation and are characterized by [F2,N]/[F1,N]=(0.89±0.06) ×N/(N + 1). The Λ-doublet distributions for 18OH (all N) and 16OH (low-to-moderate N) fragments conform to an unconstrained-dynamics prior distribution. A slight propensity for Π(A') in excess of this expectation is seen for the 16OH (high N) fragments. These new results are discussed in terms of possible insertion and abstraction mechanisms for the reaction.

Notes: Nonadiabatic interactions in the NeICl van der Waals complex have been explored in the lowest energy triad of ICl ion-pair states (∼39 000 cm−1). Dispersed fluorescence measurements reveal emission characteristic of multiple ion-pair electronic states, with the relative contributions from the E(0+), β(1), and D'(2) states changing with the initial ICl vibrational excitation (vICl). Emission directly from NeICl (vICl=0) complexes indicates that the initially prepared NeICl levels have mixed electronic character and that the ICl electronic parentage changes with the initial van der Waals vibrational level selected. NeICl complexes prepared with 1–4 quanta of ICl stretch undergo rapid vibrational predissociation with a strong propensity for ΔvICl=−1 relaxation. The electronic state(s) populated in the ICl fragments differ from the mixed electronic character of the initially prepared level, demonstrating that vibrational predissociation is accompanied by nonadiabatic electronic state changing processes. The observed final state selectivity may be attributed to the relative strength of the nonadiabatic couplings between the initial NeICl bound state and the final ICl states or a momentum gap rationale based on the overlap between the NeICl bound state wave function and the highly oscillatory continuum wave function of the separating fragments.

Notes: The transient infrared response of CO/Pt(111) following picosecond visible excitation is reported. A spectrally broad decrease in reflectivity correlates with heating of the Pt lattice, and an observed shift in the CO(v=0→1) transition is interpreted as heating of the 60 cm−1 in-plane frustrated translational mode. A phenomenological three temperature model that assumes the adsorbate vibrational temperature Tads exclusively couples to either the electronic temperature Te (with a time constant τe) or to the lattice temperature Tlat (with a time constant τlat) describes the temporal response of the adsorbate vibrations. The lattice phonon temperature Tlat(z,t) and measured temperature dependence of the optical constants predict the observed spectrally broad reflectivity change. Density matrix methods model the infrared response of the transiently heated molecule. Limits of τe=2±1 ps or τlat〈1 ps are established by comparison of predicted spectra and the data.

Notes: The assessment of signal to noise (S/N) values in x-ray absorption spectroscopy is important for a number of reasons. Two methods will be described that remove the signal to give the noise. The first uses polynomials and the second Fourier filtering. Having extracted the noise the signal can then be used to calculate the S/N ratio. The method described operates on a background subtracted spectrum and is quick so it can be done on line in an experimental situation.

Notes: Coexisting Ca-poor and Ca-rich pyroxenes in granulites at Cape Riche, in the Precambrian Albany-Fraser Province, Western Australia, are dominantly chemically homogeneous within individual samples, suggesting a major episode of equilibration. However, occasional grains in a few samples contain exsolved domains interpreted as relics of an earlier, higher-T assemblage. Pyroxene pairs in ten, presumably isothermal, samples from a restricted area are used to (i) assess the suitability of several versions of the two-pyroxene thermometer for application to metamorphic rocks, and (ii) determine the thermal history of the Cape Riche pyroxenes.The various versions of the two-pyroxene thermometer applied to the well-equilibrated homogeneous pyroxene grains show poor to good precision and yield mean temperatures varying widely from 683° to 893°C, in the following order of increasing T: Lindsley (1983; opx version), 683°± 11°C; Kretz (1982; KD version), 705°± 19°C; Ross & Huebner (1975), 709°± 30°C; Kretz (1982; solvus version), 735°± 24°C; Fonarev & Graphchikov (1982; opx version), 〈750°C; Lindsley (1983; cpx version), 784°± 40°C; Fonarev & Graphchikov (1982; cpx version), ~820°± 30°C; Wood & Banno (1973), 849°± 16°C; Powell (1978), 854°± 23°C; Wells (1977), 893°± 10°C. Independent T estimates, based on mafic assemblages and garnet-biotite thermometry, suggest that the major episode of metamorphism occurred at 700-800°C (P ~ 5 kbar). Therefore the Wells, Powell, Wood & Banno and Fonarev & Graphchikov (cpx) temperatures are almost certainly too high. In the absence of a more precise independent T estimate it is difficult to assess the relative merits of the results obtained from the remaining versions of the two-pyroxene thermometer, none of which can be unequivocally demonstrated to be seriously in error, though the Lindsley (opx) T is probably too low. Other significant shortcomings evident in the results include the relatively poor precision obtained from the three methods based on purely graphical representation of the augite limb of the solvus (i.e., the Ross & Huebner, Fonarev & Graphchikov (cpx) and Lindsley (cpx) versions), and the apparent dependence of derived T on Mg/Fe2+ ratio for the Powell, Wood & Banno and Lindsley (cpx) methods.For the bulk compositions of exsolved domains, the different versions of the two-pyroxene thermometer yield mean temperatures 23° to 82°C (overall mean, 65°C) higher than for homogeneous grains in the same samples. These exsolved domains are interpreted as relics of a higher-T (peak?) metamorphic assemblage, rather than an igneous precursor.

Notes: It is widely believed that large size creates problems for industrial relations and, conversely, that small size is beneficial. There has been little research relating size and workers' attitudes—this article reports the findings from a study in 24 factories in British manufacturing industry.

Notes: In this article the author assesses the difficulties facing democracy in the British Retail Co-operative Movement, with special reference to the role of employees on boards of directors.

Notes: A high-power proportional temperature controller, using a fast infrared pyrometer, has been developed to change and control the temperature of metallic ribbon samples with microsecond response. The apparatus provides uniform and controlled heating for time-resolved x-ray scattering studies of structural phase transitions. When high-power pulse heating is used, the system is capable of increasing the sample temperature at rates in excess of 106 K/s, without overshoot and with subsequent control to ±1 K at temperatures as low as 650 K.