Publication Date

2011-11-15

Availability

Open access

Embargo Period

2011-11-15

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PHD)

Department

Marine and Atmospheric Chemistry (Marine)

Date of Defense

2011-11-04

First Committee Member

Anthony J. Hynes

Second Committee Member

Elliot L. Atlas

Third Committee Member

Daniel D. Riemer

Fourth Committee Member

Rod G. Zika

Fifth Committee Member

Nancy L. Garland

Abstract

Formaldehyde (HCHO) plays a primary role in tropospheric chemistry. Its photochemical activity is an important source of radical species such as HCO, H, and subsequently HO2 as well as molecular hydrogen and carbon monoxide. As a source of hydrogen radicals (HOx = OH + HO2), HCHO plays a significant role in the oxidative capacity of the atmosphere, and an important part in the interrelated chemistries of ozone and the HOx and NOx (NO + NO2) cycles. Accurate atmospheric photolysis rates of HCHO are thus required in order to properly model tropospheric chemistry. Despite extensive studies HCHO’s spectroscopy and photochemistry remains to be well characterized. Absolute room temperature absorption cross sections for the A1A2 – X1A1 electronic transition of formaldehyde have been measured over the spectral range 30285 – 32890 cm-1 (304 – 330 nm) using ultraviolet (UV) laser absorption spectroscopy. Absorption cross sections were obtained at an instrumental resolution better than 0.09 cm-1 which is slightly broader than the Doppler width of a rotational line of HCHO at 300K (~0.07 cm-1) and so we were able to resolve all but the most closely spaced lines. Qualitative comparisons with spectral simulations show varying agreement depending on vibronic band. Refined state origins and transition dipole moments for each vibronic band have been reported. There is evidence of areas of perturbation and the need to optimize higher order spectral constants. Pressure broadening parameters have been measured and increase with the strength of intermolecular interaction between formaldehyde and the collision partner. Comparisons between the available high-resolution studies and spectral simulations indicate that the HCHO absorption cross section is still not well characterized. The relative quantum yield for the production of radical products, H+HCO, from the UV photolysis of formaldehyde (HCHO) has been measured directly using a Pulsed Laser Photolysis – Pulsed Laser Induced Fluorescence (PLP – PLIF) technique across the same spectral region. Relative yields were normalized to a value of 0.69 at 31750 cm-1 based on the current NASA-JPL recommendation. The resulting absolute radical quantum yields agree well with previous experimental studies and show more wavelength dependent behavior than the recommendation. This provides support for the complicated competition among the various HCHO dissociation pathways.

Keywords

formaldehyde, photochemistry, spectroscopy, absorption cross sections, quantum yields, atmospheric chemistry

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