Experimental and theoretical investigation of correlated fine structure branching ratios arising from state-selected predissociation of BrO (A2Π3/2).

We present results for the v'-dependent predissociation dynamics of the BrO (A(2)Π3/2) state using velocity map ion imaging. Correlated fine structure branching ratios, Br((2)P(J)) + O((3)P(J)), have been measured for v' = 5-16 states. The experimental branching ratios are non-statistical and strongly dependent on the initial vibronic state. The current measurements represent an extensive dataset containing rich information about the predissociation dynamics of this system and should provide a stringent test for modern theory. New high level ab initio excited state potentials are presented and have been optimized using experimental v'-dependent predissociation lifetimes and calculated coupling constants. Comparisons between the experimental branching ratios and the predictions based on diabatic and adiabatic limiting models are presented. We find that the adiabatic model is most consistent with the observed trends in the correlated branching ratios, in contrast to previous studies on the related ClO system.

Isomer-selective study of the OH initiated oxidation of isoprene in the presence of O(2) and NO. I. The minor inner OH-addition channel.

We report isomer-selective kinetics and mechanistic details for the hydroxyl radical-initiated oxidation of isoprene, in the presence of O(2) and NO, employing complementary experimental and theoretical techniques. Using a recently demonstrated photolytic route to initiate isomer-selective kinetics in OH-initiated oxidation of unsaturated hydrocarbons via the UV photolysis of iodohydrins, the photolysis of 1-iodo-2-methyl-3-buten-2-ol results in a single isomer of the possible four OH-isoprene adducts, specifically the minor channel associated with OH addition to one of the inner carbon atoms. Employing both the laser-photolysis/laser-induced fluorescence (LP/LIF) technique and time-dependent multiplexed photoionization mass spectrometry, we find clear experimental evidence supporting the prompt rearrangement of the initially formed beta-hydroxyalkyl radicals to alpha-hydroxyalkyl radicals, in agreement with Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation predictions. We have determined a rate constant of (3.3 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) for molecular oxygen to abstract a hydrogen atom from the alpha-hydroxyalkyl radical to form 4-penten-2-one and HO(2). This reaction provides a mechanistic route to C(5) carbonyl species as first-generation end products for the addition of hydroxyl radical to isoprene in the presence of O(2) and NO.

Correlated fine structure branching ratios arising from state-selected predissociation of ClO (A 2Pi 3/2).

We have extended our investigation of the v'-dependent predissociation dynamics of the ClO A(2)Pi(3/2) state using velocity-map ion imaging. Correlated fine-structure branching ratios are reported for v' = 0-5. The measured branching ratios are non-statistical and are qualitatively inconsistent with adiabatic dissociation dynamics. The coupling constants between the A(2)Pi(3/2) state and several dissociative excited state potentials have been optimized, as have the locations of the crossing points, based on comparison to previously reported v'-dependent predissociation rates. Using these optimized potentials we have modeled the branching ratios in the diabatic limit but the lack of agreement with experiments suggests the importance of exit channel coupling. Coupled channel calculations including 9 coupled potentials provide modest improvement with experiment but differences remain.

Anisotropy of photofragment recoil as a function of dissociation lifetime, excitation frequency, rotational level, and rotational constant.

Quantum mechanical calculations of photofragment angular distributions have been performed as a function of the frequency of excitation, the lifetime of the dissociative state, the rotational level, and the rotational constant. In the limit of high J values and white, incoherent excitation, the general results are found to agree exactly with both those of Mukamel and Jortner [J. Chem. Phys. 61, 5348 (1974)] and those of Jonah [J. Chem. Phys. 55, 1915 (1971)]. Example calculations describe how the anisotropy is dependent on the degree of broadening, the rotational constant, the initial rotational level, and the frequency of excitation. Applications are also made to interpret experimental results on the photodissociation of ClO via the 11-0, 10-0, and 6-0 bands of the A 2Pi3/2 -X 2Pi3/2 transition and on the photodissociation of O2 via the 0-0 band of the E 3Sigmau- -X 3Sigmag- transition.

Vibrational state-dependent predissociation dynamics of ClO (A (2)Pi(3/2)): Insight from correlated fine structure branching ratios.

We have studied the v'-dependent predissociation dynamics of the ClO A (2)Pi(3/2) state using velocity-map ion-imaging. Experimental final correlated state branching ratios, i.e. Cl((2)P(J=3/2,1/2)) + O((3)P(J=2,1,0)) channels, have been measured for v' = 6-11. We find that the branching ratios are highly variable and depend strongly on v', providing a window into the v'-dependent predissociation mechanism. A comparison of the experimental results with the recent model of Lane et al. (I. C. Lane, W. H. Howie and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 1999, 1, 3087) in both the diabatic and adiabatic limits suggests that the dynamics are closer to the diabatic limit. The overall Cl((2)P(J)) branching ratios are in good agreement with the diabatic model results. There are significant differences, however, between theory and experiment at the correlated state level, demonstrating the sensitivity of correlated measurements to the role of the exit channel coupling in the predissociation dynamics. The results highlight the need for more sophisticated quantum dynamical calculations to describe the correlated fine structure branching ratios in this system.

Photodissociation of the BrO radical using velocity map ion imaging: excited state dynamics and accurate D0(0)(BrO) evaluation.

We have studied the photodissociation dynamics of expansion-cooled BrO radical both above (278-281.5 nm) and below (355 nm) the A (2)Pi(3/2) state threshold using velocity map ion imaging. A recently developed late-mixing flash pyrolytic reactor source was utilized to generate an intense BrO radical molecular beam. The relative electronic product branching ratios at 355 nm and from 278 to 281.5 nm were determined. We have investigated the excited state dynamics based on both the product branching and the photofragment angular distributions. We find that above the O((1)D(2)) threshold the contribution of the direct excitation to states other than the A (2)Pi(3/2) state and the role of curve crossing is considerably larger in BrO compared to that observed for ClO, in agreement with recent theoretical studies. The measurement of low velocity photofragments resulting from photodissociation just above the O((1)D(2)) threshold provides an accurate and direct determination of the A (2)Pi(3/2) state dissociation threshold of 35418+/-35 cm(-1), leading to a ground state bond energy of D(0)(0)(BrO)=55.9+/-0.1 kcal/mol.