PNNL

Abstract

Absolute intensities, self- and air-broadening coefficients, self- and air-induced shift coefficients and their temperature dependences have been determined for lines belonging to the P and R branches of the v2 band of H12C14N centered near 712 cm-1. Infrared spectra of HCN in the 14- vm region were obtained at high resolution (0.002-0.008 cm-1) using two different Fourier transform spectrometers (FTS), the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak and the Bruker IFS 120HR FTS at the Pacific Northwest National Laboratory. Spectra were recorded with 99.8% pure HCN as well as lean mixtures of HCN in air at various temperatures ranging between +26ºC and –60ºC. A multispectrum nonlinear least squares technique was used to fit selected intervals of 36 spectra simultaneously to obtain the line positions, intensities, broadening and shift parameters. The measured line intensities were analyzed to determine the vibrational band intensity and the Herman-Wallis coefficients. The measured self-broadening coefficients vary between 0.2 and 1.2 cm-1 atm-1 at 296 K, and the air broadening Absolute intensities, self- and air-broadening coefficients, self- and air-induced shift coefficients and their temperature dependences have been determined for lines belonging to the P and R branches of the v2 band of H12C14N centered near 712 cm-1. Infrared spectra of HCN in the 14- vm region were obtained at high resolution (0.002-0.008 cm-1) using two different Fourier transform spectrometers (FTS), the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak and the Bruker IFS 120HR FTS at the Pacific Northwest National Laboratory. Spectra were recorded with 99.8% pure HCN as well as lean mixtures of HCN in air at various temperatures ranging between +26ºC and –60ºC. A multispectrum nonlinear least squares technique was used to fit selected intervals of 36 spectra simultaneously to obtain the line positions, intensities, broadening and shift parameters. The measured line intensities were analyzed to determine the vibrational band intensity and the Herman-Wallis coefficients. The measured self-broadening coefficients vary between 0.2 and 1.2 cm-1 atm-1 at 296 K, and the air broadening coefficients range from 0.08 to 0.14 cm-1 atm-1 at 296 K. The temperature dependence exponents of self-broadening range from 1.46 to –0.12 while the corresponding exponents for air broadening vary between 0.58 and 0.86. The present measurements are the first known determination of negative values for the temperature dependence exponents of HCN broadening coefficients. We were able to support our self-broadening measurements with appropriate theoretical calculations. Our present measurements are compared, where possible, with previous measurements for this and other HCN bands, as well as the parameters that are included in the 2000 and 2004 editions of the HITRAN (HIgh-resolution TRANsmission) database.