Rotationally resolved absorption cross sections of formaldehyde in the 28100-28500 cm -1 (351-356 nm) spectral region: Implications for in situ LIF measurements

Dick T. Co, Thomas F. Hanisco, James G. Anderson, Frank N. Keutsch

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The rotationally resolved ultraviolet absorption cross sections for the 2 0 04 0 1 vibrational band of the A 1A 2-X 1A 1 electronic transition of formaldehyde (HCHO) at an apodized resolution of 0.027 cm -1 (approximately 0.0003 nm at 352 nm) over the spectral range 28100-28500 cm -1 (351-356 nm) at 298 and 220 K, using Fourier transform spectroscopy, are first reported here. Accurate rotationally resolved cross sections are important for the development of in situ HCHO laser-induced fluorescence (LIF) instruments and for atmospheric monitoring. Pressure dependence of the cross sections between 75 and 400 Torr at 298 K was explored, and an average pressure broadening coefficient in dry air of 1.8 × 10 -4 cm -1 Torr -1 for several isolated lines is reported. Gaseous HCHO was quantitatively introduced into a flow cell by evaporating micronsized droplets of HCHO solution, using a novel microinjector technique. The condensed-phase concentrations of HCHO were determined by iodometric titrations to an accuracy of <1%. Accuracy of the measured absorption cross sections is estimated to be better than ±5%. Integrated and differential cross sections over the entire band at low resolution (∼1 cm -1) obtained with our calibration technique are in excellent agreement with previous measurements. A maximum differential cross section of 5.7 × 10 -19 cm 2 molecule -1 was observed at high resolution-almost an order of magnitude greater than any previously reported data at low resolution.

Original languageEnglish
Pages (from-to)10675-10682
Number of pages8
JournalJournal of Physical Chemistry A
Issue number47
Publication statusPublished - Dec 1 2005


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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