The National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) are each creating quantitative databases containing the vapor-phase infrared spectra of pure chemicals. The digital databases have been created with both laboratory and remote-sensing applications in mind. A spectral resolution of approximate, equals 0.1 cm(-1) was selected to avoid degrading sharp spectral features, while also realizing that atmospheric broadening typically limits line widths to 0.1 cm(-1). Calculated positional (wave- number, cm(-1)) uncertainty is /=9) path length-concentration burdens and fitting a weighted Beer's law plot to each wavenumber channel. The two databases include different classes of compounds and were compared using 12 samples. Though these 12 samples span a range of polarities, absorption strengths, and vapor pressures, the data agree to within experimental uncertainties with only one exception.

With the recent developments in Fourier transform infrared (FTIR) spectrometers it is becoming more feasible to place these instruments in field environments. As a result, there has been enormous increase in the use of FTIR techniques for a variety of qualitative and quantitative chemical measurements. These methods offer the possibility of fully automated real-time quantitation of many analytes; therefore FTIR has great potential as an analytical tool. Recently, the U.S. Environmental Protection Agency (U.S.EPA) has developed protocol methods for emissions monitoring using both extractive and open-path FTIR measurements. Depending upon the analyte, the experimental conditions and the analyte matrix, approximately 100 of the hazardous air pollutants (HAPs) listed in the 1990 U.S.EPA Clean Air Act amendment (CAAA) can be measured. The National Institute of Standards and Technology (NIST) has initiated a program to provide quality-assured infrared absorption coefficient data based on NIST prepared primary gas standards. Currently, absorption coefficient data has been acquired for approximately 20 of the HAPs. For each compound, the absorption coefficient spectrum was calculated using nine transmittance spectra at 0.12 cm−1 resolution and the Beer’s law relationship. The uncertainties in the absorption coefficient data were estimated from the linear regressions of the transmittance data and considerations of other error sources such as the nonlinear detector response. For absorption coefficient values greater than 1 × 10−4 μmol/mol)−1 m−1 the average relative expanded uncertainty is 2.2 %. This quantitative infrared database is currently an ongoing project at NIST. Additional spectra will be added to the database as they are acquired. Our current plans include continued data acquisition of the compounds listed in the CAAA, as well as the compounds that contribute to global warming and ozone depletion.

The reaction between ground state atomic oxygen and ethylene was studied under single collision conditions using the crossed molecular beam method. At an average collision energy of about 6 kcal/mol, the two major primary reaction channels are (a) the formation of CH3 and CHO and (b) the formation of C2H3O and H. Product angular distributions and time-of-flight spectra were measured and the translational energy release was determined for each channel. The observed results and calculated potential energy surfaces suggest that after the addition of O(3P) to ethylene forming a triplet diradical, channel (a) occurs by way of intersystem crossing to the singlet state, 1,2-H migration and subsequent C–C bond rupture, whereas channel (b) proceeds mostly through the direct dissociation of the intermediate triplet diradical, except for a small contribution from H atom elimination of the singlet acetaldehyde intermediate.

The reaction between ground state atomic oxygen and acetylene was studied using the crossed molecular beam method with an average collision energy of 6 kcal/mol. The two major primary reaction channels are (a) formation of CH2 and CO and (b) formation of HCCO and H. Product angular distributions and time-of-flight spectra were measured and the translational energy release was determined for each channel. The reaction proceeds primarily on the triplet surface through a long-lived intermediate. For both channels the translational energy distributions were found to peak at about 30% of the total available energy, indicating the existence of an exit channel barrier in each case. The branching ratio between channel (a) and (b) was found to be 1.4±0.5.