title: High-resolution absorption studies of the A(1)A2-X(1)A1 2(0)(2)4(0)(1) band of formaldehyde.
abstract: Absolute peak absorption cross sections and pressure broadening coefficients have been recorded with sub-Doppler limited instrumental resolution for selected rotational lines in the 2(0)(2)4(0)(1) vibronic band of the formaldehyde A(1)A2-X(1)A1 electronic transition. The measured absorption cross sections range between (0.18 +/- 0.01) and (10.1 +/- 0.08) x 10(-19) cm2 molecule(-1) and are considerably larger than values from the literature recorded using apparatus where instrumental broadening was significant. However, comparisons with spectral simulations with equivalent resolution from Smith et al. (J. Phys. Chem. A 2006, 110, 11645-11653) are in excellent agreement. Pressure broadening was studied for the collision partners CH2O, CO2, N2, O2, Ne, Kr, Ar, and He, and the resulting broadening coefficients were found to be reduced in comparison to equivalent values measured in infrared regions, consistent with the reduced dipole moment of the upper state probed in this work. Cavity-enhanced absorption spectroscopy (CEAS) measurements were undertaken using calibrated low concentration (2.9-4.6 ppmv) samples from a permeation source and demonstrate a noise equivalent absorption of 1.2 x 10(-6) cm(-1) Hz(-1/2). This implies a minimum detectable formaldehyde concentration with the current system in atmospheric air of 172 ppbv Hz(-1/2).
authors.affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, UK.
authors.forename: Martin B
authors.initials: MB
authors.lastname: Crow
authors.forename: Alex
authors.initials: A
authors.lastname: Gilchrist
authors.forename: Gus
authors.initials: G
authors.lastname: Hancock
authors.forename: Rob
authors.initials: R
authors.lastname: Peverall
authors.forename: Graham
authors.initials: G
authors.lastname: Richmond
authors.forename: Grant A D
authors.initials: GA
authors.lastname: Ritchie
authors.forename: Sarah R
authors.initials: SR
authors.lastname: Taylor