A reference high-pressure CO2 adsorption isotherm for ammonium ZSM-5 zeolite: results of an interlaboratory study.

This paper reports the results of an international interlaboratory study led by the National Institute of Standards and Technology (NIST) on the measurement of high-pressure surface excess carbon dioxide adsorption isotherms on NIST Reference Material RM 8852 (ammonium ZSM-5 zeolite), at 293.15 K (20 °C) from 1 kPa up to 4.5 MPa. Eleven laboratories participated in this exercise and, for the first time, high-pressure adsorption reference data are reported using a reference material. An empirical reference equation n e x = d ( 1 + exp [ - ln ( P ) + a / b ] ) c , [n ex -surface excess uptake (mmol/g), P-equilibrium pressure (MPa), a = -6.22, b = 1.97, c = 4.73, and d = 3.87] along with the 95% uncertainty interval (U k = 2 = 0.075 mmol/g) were determined for the reference isotherm using a Bayesian, Markov Chain Monte Carlo method. Together, this zeolitic reference material and the associated adsorption data provide a means for laboratories to test and validate high-pressure adsorption equipment and measurements. Recommendations are provided for measuring reliable high-pressure adsorption isotherms using this material, including activation procedures, data processing methods to determine surface excess uptake, and the appropriate equation of state to be used.

Comb-linked, cavity ring-down spectroscopy for measurements of molecular transition frequencies at the kHz-level.

We present a low uncertainty measurement technique for determining molecular transition frequencies. This approach is complementary to sub-Doppler saturation spectroscopies and is expected to enable new frequency measurements for a wide variety of molecular species with uncertainties at the kHz-level. The technique involves measurements of Doppler broadened lines using cavity ring-down spectroscopy whereby the probe laser is actively locked to the ring-down cavity and the spectrum frequencies are linked directly to an optical frequency comb that is referenced to an atomic frequency standard. As a demonstration we have measured the transition frequency of the (30012) ← (00001) P14e line of CO2 near 1.57 µm with a combined standard uncertainty of ~9 kHz. This technique exhibits exceptional promise for measurements of transition frequencies and pressure shifting parameters of many weak absorbers, and indicates the potential for substantially improved measurements when compared to those obtained with conventional spectroscopic methods.

Fermi level alignment in self-assembled molecular layers: the effect of coupling chemistry.

Photoelectron spectroscopy was used to explore changes in Fermi level alignment, within the pi-pi* gap, arising from modifications to the coupling chemistry of conjugated phenylene ethynylene oligomers to the Au surface. Self-assembled monolayers were formed employing either thiol (4,4'-ethynylphenyl-1-benzenethiol or OPE-T) or isocyanide (4,4'-ethynylphenyl-1-benzeneisocyanide or OPE-NC) coupling. The electronic density of states in the valence region of the two systems are nearly identical with the exception of a shift to higher binding energy by about 0.5 eV for OPE-NC. Corresponding shifts appear in C(1s) spectra and in the threshold near E(F). The lack of change in the optical absorption suggests that a rigid shift of the Fermi level within the pi-pi* gap is the major effect of modifying the coupling chemistry. Qualitative consideration of bonding in each case is used to suggest the influence of chemisorption-induced charge transfer as a potential explanation. Connections to other theoretical and experimental work on the effects of varying coupling chemistries are also discussed.

Pulsed, single-mode cavity ringdown spectroscopy.

We discuss the use of single-mode cavity ringdown spectroscopy with pulsed lasers for quantitative gas density and line strength measurements. The single-mode approach to cavity ringdown spectroscopy gives single exponential decay signals without mode beating, which allows measurements with uncertainties near the shot-noise limit. The technique is demonstrated with a 10-cm-long ringdown cavity and a pulsed, frequency-stabilized optical parametric oscillator as the light source. A noise-equivalent absorption coefficient of 5 x 10(-10) cm(-1) Hz(-1/2) is demonstrated, and the relative standard deviation in the ringdown time (sigma(tau)/tau) extracted from a fit to an individual ringdown curve is found to be the same as that for an ensemble of hundreds of independent measurements. Repeated measurement of a line strength is shown to have a standard deviation <0.3%. The effects of normally distributed noise on quantities measured using cavity ringdown spectroscopy are discussed, formulas for the relative standard deviation in the ringdown time are given in the shot- and technical-noise limits, and the noise-equivalent absorption coefficient in these limits are compared for pulsed and continuous-wave light sources.

Laser bandwidth effects in quantitative cavity ring-down spectroscopy.

We have investigated the effects of laser bandwidth on quantitative cavity ring-down spectroscopy using the (r)R transitions of the b(ν = 0)?X(ν = 0) band of molecular oxygen. It is found that failure to account properly for the laser bandwidth leads to systematic errors in the number densities determined from measured ring-down signals. When the frequency-integrated expression for the ring-down signal is fitted and measured laser line shapes are used, excellent agreement between measured and predicted number densities is found.