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Absolute quantum yields for the radical (H + HCO) channel of HCHO photolysis, Phi(HCO), have been measured for the tropospherically relevant range of wavelengths (lambda) between 300 and 330 nm. The HCO photoproduct was directly detected by using a custom-built, combined ultra-violet (UV) absorption and cavity ring down (CRD) detection spectrometer. This instrument was previously employed for high-resolution (spectral resolution approximately 0.0035 nm) measurements of absorption cross-sections of HCHO, sigma(HCHO)(lambda), and relative HCO quantum yields. Absolute Phi(HCO) values were measured at seven wavelengths, lambda = 303.70, 305.13, 308.87, 314.31, 320.67, 325.59, and 329.51 nm, using an independent calibration technique based on the simultaneous UV photolysis of HCHO and Cl(2). These Phi(HCO) measurements display greater variability as a function of wavelength than the current NASA-JPL recommendations for Phi(HCO). The absolute Phi(HCO)(lambda) determinations and previously measured sigma(HCHO)(lambda) were used to scale an extensive set of relative HCO yield measurements. The outcome of this procedure is a full suite of data for the product of the absolute radical quantum yield and HCHO absorption cross-section, Phi(HCO)(lambda)sigma(HCHO)(lambda), at wavelengths from 302.6 to 331.0 nm with a wavelength resolution of 0.005 nm. This product of photochemical parameters is combined with high-resolution solar photon flux data to calculate the integrated photolysis rate of HCHO to the radical (H + HCO) channel, J(HCO). Comparison with the latest NASA-JPL recommendations, reported at 1 nm wavelength resolution, suggests an increased J(HCO) of 25% at 0 degrees solar zenith angle (SZA) increasing to 33% at high SZA (80 degrees). The differences in the calculated photolysis rate compared with the current HCHO data arise, in part, from the higher wavelength resolution of the current data set and highlight the importance of using high-resolution spectroscopic techniques to achieve a complete and accurate picture of HCHO photodissociation processes. All experimental Phi(HCO)(lambda)sigma(HCHO)(lambda) data are available for the wavelength range 302.6-331.0 nm (at 294 and 245 K and under 200 Torr of N(2) bath gas) as Supporting Information with wavelength resolutions of 0.005, 0.1, and 1.0 nm. Equivalent data sets of Phi(H(2)+CO)(lambda)sigma(HCHO)(lambda) for the molecular (H(2) + CO) photofragmentation channel, produced using the measured Phi(HCO)(lambda) sigma(HCHO)(tau) values, are also provided at 0.1 and 1.0 nm resolution.

Absorption cross sections for the A1A2-X1A1 electronic transition of formaldehyde have been measured by ultraviolet (UV) laser absorption spectroscopy in the tropospherically significant wavelength range 300-340 nm, over which HCHO is photochemically active. Absorption cross sections are reported at two temperatures, 294 and 245 K and at a spectral resolution of 0.0035 nm (0.35 cm-1). At this resolution, greater peak absorption cross sections are obtained for many of the sharp spectral features than were previously reported. To simulate atmospheric conditions in the troposphere, the effects of adding a pressure of nitrogen of up to 500 Torr and of reduced sample temperature were investigated. The overall magnitudes of peak absorption cross sections are largely unaffected by the added pressure of nitrogen, but a modest degree of pressure broadening (0.2-0.3 cm-1 atm-1) is evident in the line shapes. Computer simulations of spectra have been optimized by comparison with wavelength-dependent formaldehyde absorption cross sections for each major vibronic band in the chosen wavelength range. Experimental and computer simulated spectra at 294 and 245 K are compared to test the reliability of the computer simulations for quantification of the effects of temperature on absorption cross sections. All experimental absorption cross section data and tables of input parameters for spectral simulations are available as Supporting Information.