Pulsed laser photolysis (PLP) at λ=248 and 308 nm coupled with gas-chromatographic analysis is applied to determine the photodissociation quantum yield (QY) of methyl ethyl ketone (MEK). Temperature dependent UV absorption cross-sections [σ(MEK)(λ,T)] are also determined. At 308 nm, the QY decreases with decreasing temperature (T=323-233 K) and with increasing pressure (P=67-998 mbar synthetic air). Stern-Volmer (SV) analysis of the T and P dependent QYs provides the experimental estimate of E(S1)=398±9 kJ mol(-1) (=300±6 nm) for the barrier of the first excited singlet state (S(1)). The QY at 248 nm is close to unity and independent of pressure (T=298 K). Theoretical reaction pathways are examined systematically on the basis of CASPT2/6-31+G* calculations. Among three possible pathways, a S(1)/S(0)-diradical mechanism, which involves H atom transfer on the S(1) surface, followed by a nonadiabatic transition at a diradical isomer of MEK, explains the experimental data very well. Therefore, this unusual mechanism, which is not seen in any smaller carbonyl compounds, is proposed as an important pathway for the MEK dissociation. Our study supports the view that both the absorption cross-sections and the QYs of carbonyls have significant temperature dependences that should be taken into account for accurate modelling of atmospheric chemistry.

The pressure dependence of the photodissociation quantum yield of acetone has been determined in different buffer gases at 308 nm. Results by Stern-Volmer analyses are in accordance with a suggested photolysis mechanism. Luminescence spectra, lifetimes and transition dipole moments have been determined. The energy transfer process by O 2 to give O 2 ( 1 ∆ g ) is of minor importance in the case of the singlet excited state of acetone, while it is the dominant deactivation process for the triplet state.

ABSTRACT:The direct reaction kinetic method of low pressure fast discharge flow (DF) with resonance fluorescence monitoring of OH (RF) has been applied to determine rate coefficients for the overall reactions OH + C 2 H 5 F (EtF) (1) and OH + CH 3 C(O)F (AcF) (2). Acetyl fluoride reacts slowly with the hydroxyl radical, the rate coefficient at laboratory temperature is k2 (300 K) = (0.74 ± 0.05) × 10 -14 cm 3 molecule -1 s -1 (given with 2σ statistical uncertainty). The temperature dependence of the reaction does not obey the Arrhenius law and it is described well by the two-exponential rate expression of k 2 (300-410 K) = 3.60 × 10 -3 exp(-10500 / T) + 1.56 × 10 -13 exp(-910 / T) cm 3 molecule -1 s -1 . The rate coefficient of k 1 = (1.90 ± 0.19) × 10 -13 cm 3 molecule -1 s -1 has been determined for the EtF-reaction at room temperature (T = 298 K).Microscopic mechanisms for the OH + CH 3 C(O)F reaction have also been studied theoretically using the ab initio CBS-QB3 an G4 methods. Variational transition state theory was employed to obtain rate coefficients for the OH + CH 3 C(O)F reaction as a function of temperature on the basis of the ab initio data. The calculated rate coefficients are in good agreement with the experimental data. It is revealed that the reaction takes place predominantly via the indirect H-abstraction mechanism involving H-bonded prereactive complexes and forming the nascent products of H 2 O and the CH 2 CFO radical. The nonArrhenius behavior of the rate coefficient at temperatures below 500 K is ascribed to the significant tunneling effect of the in-the-plane H-abstraction dynamic bottleneck. The production of FC(O)OH + CH 3 via the addition/elimination mechanism is hardly competitive due to the significant barriers along the reaction routes.Photochemical experiments of AcF were performed at 248 nm by using exciplex lasers. The total photodissociation quantum yield for CH 3 C(O)F has been found significantly less than unity; among the primary photochemical processes, C-C bond cleavage is by far dominating compared with CO-elimination. The absorption spectrum of AcF has also been determined displaying a strong blue shift compared with the spectra of aliphatic carbonyls.Consequences of the results on atmospheric chemistry have been discussed.3