Theory of multichannel thermal unimolecular reactions. 2. Application to the thermal dissociation of formaldehyde

The thermal dissociation of formaldehyde proceeds on three channels, the molecular-elimination channel H2CO --> H2 + CO (1), the radical-forming bond-fission channel H2CO --> H + HCO (2), and the bond-fission-initiated, intramolecular-hydrogen-abstraction channel H2CO --> H...HCO --> H2 + CO (3) which also forms molecular products. The kinetics of this system in the low-pressure range of the unimolecular reaction is shown to be governed by a subtle superposition of collisional channel coupling to be treated by solving a master equation, of rotational channel switching accessible through ab initio calculations of the potential as well as spectroscopic and photophysical determinations of the threshold energies and channel branching above the threshold energy for radical formation which can be characterized through formaldehyde photolysis quantum yields as well as classical trajectory calculations. On the basis of the available information, the rate coefficients for the formation of molecular and radical fragments are analyzed and extrapolated over wide ranges of conditions. The modeled rate coefficients in the low-pressure range of the reaction (neglecting tunneling) over the range 1400-3200 K in the bath-gas Ar in this way are represented by k0,Mol/Ar] approximately 9.4 x 10(-9) exp(-33,140 K/T) cm3 molecule(-1) s(-1) and k0,Rad/Ar] approximately 6.2 x 10(-9) exp(-36,980 K/T) cm3 molecule(-1) s(-1). The corresponding values for the bath-gas Kr, on which the analysis relies in particular, are k0,Mol/Kr] approximately 7.7 x 10(-9) exp(-33,110 K/T) and k0,Rad/Kr] approximately 4.1 x 10(-9) exp(-36 910 K/T) cm3 molecule(-1) s(-1). While the threshold energy E0,2 for channels 2 and 3 is taken from spectroscopic measurements, the threshold energy E0,1 for channel 1 is fitted on the basis of experimental ratios k0,Rad/k0,Mol in combination with photolysis quantum yields. The derived value of E0,1(1) = 81.2 (+/-0.9) kcal mol(-1) is in good agreement with results from recent ab initio calculations, 81.9 (+/-0.3) kcal mol(-1), but is higher than earlier results derived from photophysical experiments, 79.2 (+/-0.8) kcal mol(-1). Rate coefficients for the high-pressure limit of the reaction are also modeled. The results of the present work markedly depend on the branching ratio between channels 2 and 3. Expressions of this branching ratio from classical trajectory calculations and from photolysis quantum yield measurements were tested. At the same time, a modeling of the photolysis quantum yields was performed. The formaldehyde system so far presents the best characterized multichannel dissociation reaction. It may serve as a prototype for other multichannel dissociation reactions.