Excess electrons bound to H2S trimer and tetramer clusters.

We have prepared the hydrogen sulfide trimer and tetramer anions, (H2S)3- and (H2S)4-, measured their anion photoelectron spectra, and applied high-level quantum chemical calculations to interpret the results. The sharp peaks at low electron binding energies in their photoelectron spectra and their diffuse Dyson orbitals are evidence for them both being dipole-bound anions. While the dipole moments of the neutral (H2S)3 and (H2S)4 clusters are small, the excess electron induces structural distortions that enhance the charge-dipolar attraction and facilitate the binding of diffuse electrons.

Recommended practice for calibrating vacuum gauges of the ionization type.

This article represents a recommended practice for the calibration of ionization gauges using the comparison method. In this method, ionization gauges are compared to a working standard that has an SI traceable calibration. The ionization gauge is either of the hot-cathode ionization type or the cold-cathode ionization type. Details of the calibration apparatus, the principle of operation of the gauges, data analysis, uncertainty budget, and reporting the uncertainty are given.

Cell-based refractometer for pascal realization.

We describe a method for determining the density of helium via measurements of optical refractivity. In combination with the equation of state, this allows realization of the pascal. Our apparatus is based on the integration of a gas triple-cell into a quasi-monolithic heterodyne interferometer: the stability of the interferometer is ±50 pm over 10 h. We claim the contribution of cell window thinning to pathlength uncertainty can be canceled within an uncertainty of 0.37 fm/Pa per window pass, of which for our 25 cm cell length corresponds to a fractional error of 9.3×10-6 in the measure of helium refractivity. We report the ratio (n-1)N2 /(n-1)He=8.570354(13) at p=367.420(4) kPa, T=293.1529(13) K and λ=632.9908(6) nm, which can be used to calibrate less-accurate refractometers. By measuring helium refractivity at known temperature and pressure, we determined the Boltzmann constant with standard uncertainty kB=1.380652(17)×10-23 JK-1.

Comparison measurements of low-pressure between a laser refractometer and ultrasonic manometer.

We have developed a new low-pressure sensor which is based on the measurement of (nitrogen) gas refractivity inside a Fabry-Perot cavity. We compare pressure determinations via this laser refractometer to that of well-established ultrasonic manometers throughout the range 100 Pa to 180 000 Pa. The refractometer demonstrates 10(-6) ⋅ p reproducibility for p > 100 Pa, and this precision outperforms a manometer. We also claim the refractometer has an expanded uncertainty of U(pFP) = [(2.0 mPa)(2) + (8.8 × 10(-6) ⋅ p)(2)](1/2), as realized through the properties of nitrogen gas; we argue that a transfer of the pascal to p < 1 kPa using a laser refractometer is more accurate than the current primary realization.

Performance of a dual Fabry-Perot cavity refractometer.

We have built and characterized a refractometer that utilizes two Fabry-Perot cavities formed on a dimensionally stable spacer. In the typical mode of operation, one cavity is held at vacuum, and the other cavity is filled with nitrogen gas. The differential change in length between the cavities is measured as the difference in frequency between two helium-neon lasers, one locked to the resonance of each cavity. This differential change in optical length is a measure of the gas refractivity. Using the known values for the molar refractivity and virial coefficients of nitrogen, and accounting for cavity length distortions, the device can be used as a high-resolution, multi-decade pressure sensor. We define a reference value for nitrogen refractivity as n-1=(26485.28±0.3)×10(-8) at p=100.0000 kPa, T=302.9190 K, and λ(vac)=632.9908 nm. We compare pressure determinations via the refractometer and the reference value to a mercury manometer.

Lithium cluster anions: photoelectron spectroscopy and ab initio calculations.

Structural and energetic properties of small, deceptively simple anionic clusters of lithium, Li(n)(-), n = 3-7, were determined using a combination of anion photoelectron spectroscopy and ab initio calculations. The most stable isomers of each of these anions, the ones most likely to contribute to the photoelectron spectra, were found using the gradient embedded genetic algorithm program. Subsequently, state-of-the-art ab initio techniques, including time-dependent density functional theory, coupled cluster, and multireference configurational interactions methods, were employed to interpret the experimental spectra.