Following photodissociation at 248 nm of gaseous methyl formate (HC(O)OCH 3 , 0.73 Torr) and Ar (0.14 Torr), temporally resolved vibration−rotational emission spectra of highly internally excited CO (ν ≤ 11, J ≤ 27) in the 1850−2250 cm −1 region were recorded with a step-scan Fourier-transform spectrometer. The vibration−rotational distribution of CO is almost Boltzmann, with a nascent average rotational energy (E R 0 ) of 3 ± 1 kJ mol −1 and a vibrational energy (E V 0 ) of 76 ± 9 kJ mol −1 . With 3 Torr of Ar added to the system, the average vibrational energy was decreased to E V 0 = 61 ± 7 kJ mol −1 . We observed no distinct evidence of a bimodal rotational distribution for ν = 1 and 2, as reported previously [Lombardi et al., J. Phys. Chem. A 2016, 129, 5155], as evidence of a roaming mechanism. The vibrational distribution with a temperature of ∼13000 ± 1000 K, however, agrees satisfactorily with trajectory calculations of these authors, who took into account conical intersections from the S 1 state. Highly internally excited CH 3 OH that is expected to be produced from a roaming mechanism was unobserved. Following photodissociation at 193 nm of gaseous HC(O)OCH 3 (0.42 Torr) and Ar (0.09 Torr), vibration− rotational emission spectra of CO (ν ≤ 4, J ≤ 38) and CO 2 (with two components of varied internal distributions) were observed, indicating that new channels are open. Quantum-chemical calculations, computed at varied levels of theory, on the ground electronic potential-energy schemes provide a possible explanation for some of our observations. At 193 nm, the CO 2 was produced from secondary dissociation of the products HC(O)O and CH 3 OCO, and CO was produced primarily from secondary dissociation of the product HCO produced on the S 1 surface or the decomposition to CH 3 OH + CO on the S 0 surface.

We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH2OO and anti/syn-CH3C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH2OO and anti-CH3C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH3C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C-H bonds. For syn-CH3C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH3 group by the terminal O atom producing CH2C(H)O-OH. At 298 K, the intramolecular insertion process in CH2OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

The mechanism for the reaction of NCN with OH has been investigated by ab initio molecular orbital and transition-state theory calculations. The potential energy surface (PES) was calculated by the highest level of the modified GAUSSIAN-2 (G2M) method, G2M(CC1). The barrierless association process of OH + NCN --> OH...NCN (van der Waals, vdw) was also examined at the UCCSD(T)/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) and CASPT2(13,13)/ANO-L//B3LYP/6-311+G(d,p) levels. The predicted heats of reaction for the production of H + NCNO, HNC + NO, HCN + NO, and N(2) + HOC, 7.8, -53.2, -66.9, and -67.7, respectively, are in excellent agreement with the experimental values, 8.2 +/- 1.3, -52.3 +/- 1.7 (or 55.7 +/- 1.7), -66.3 +/- 0.7, and -68.1 +/- 0.7 kcal/mol. The kinetic results indicate that, in the temperature range of 300-1000 K, the formation of trans,trans-HONCN (LM2) is dominant. Over 1000 K, formation of H + NCNO is dominant, while the formation of HCN + NO becomes competitive. The rate constants for the low-energy channels given in units of cm(3) molecule(-1) s(-1) can be represented by the following: k(1)(LM2) = 1.51 x 10 (15)T(-8.72) exp(-2531/T) at 300-1500 K in 760 Torr N(2); k(2)(H+NCNO) = 5.54 x 10 (-14)T(-0.97) exp(-3669/T) and k(3)(HCN+NO) = 7.82 x 10 (-14)T(0.44) exp(-2013/T) at 300-2500 K, with the total rate constant of k(t) = 3.18 x 10 (2)T(-4.63) exp(-740/T), 300-1000 K, and k(t) = 2.53 x 10 (-14)T(1.13) exp(-489/T) in the temperature range of 1200-2500 K. These results are recommended for combustion modeling applications.