Dynamics of the reaction CHI + O probed via infrared emission of CO, CO, OH and HCO.

The reaction CH2I + O2 has been widely employed recently for the production of the simplest Criegee intermediate CH2OO in laboratories, but the detailed dynamics of this reaction have been little explored. Infrared emission of several products of this reaction, initiated on irradiation of CH2I2 and O2 (∼8 Torr) in a flowing mixture at 308 or 248 nm, was recorded with a step-scan Fourier-transform spectrometer; possible routes of formation were identified according to the observed vibrational distribution of products and published theoretical potential-energy schemes. Upon irradiation at 308 nm, Boltzmann distributions of CO (v ≤ 5, J ≤ 19) with an average vibrational energy of 32 ± 3 kJ mol-1 and OH (v ≤ 3, J ≤ 5.

Hydrogen abstraction in astrochemistry: formation of ˙CHCONH in the reaction of H atom with acetamide (CHCONH) and photolysis of ˙CHCONH to form ketene (CHCO) in solid para-hydrogen.

Acetamide (CH3CONH2) is the largest molecule containing an amide bond that has been detected in an interstellar medium; it is considered to be a precursor for complex organic molecules (COM). We utilized the advantages of a para-hydrogen (p-H2) quantum-solid matrix host to perform efficient reactions of hydrogen atoms with CH3CONH2. The H-abstraction reaction from the methyl group of CH3CONH2 to produce the 2-amino-2-oxoethyl radical, ˙CH2CONH2, was observed as the sole reaction channel in solid p-H2 at 3.

Theoretical investigations of absorption and fluorescence spectra of protonated pyrene.

The equilibrium geometry and 75 vibrational normal-mode frequencies of the ground and first excited states of protonated pyrene isomers were calculated and characterized in the adiabatic representation by using the complete active space self-consistent field (CASSCF) method. Electronic absorption spectra of solid neon matrixes in the wavelength range 495-415 nm were determined by Maier et al. and they were analyzed using time-dependent density functional theory calculations (TDDFT).

Regulation of nonadiabatic processes in the photolysis of some carbonyl compounds.

Carbonyl compounds studied are confined to acetyl halide (CH3COCl), acetyl cyanide (CH3COCN), acetyl sulfide (CH3COSH), acetaldehyde (CH3CHO), and methyl formate (HCOOCH3). They are asymmetrically substituted, but do not follow the well-known Norrish type I reactions. Each compound ejected in an effusive beam at about 300 K is commonly excited to the (1)(n, π*)CO lower state; that is, a nonbonding electron on O of the C[double bond, length as m-dash]O group is promoted to the antibonding orbital of π*CO.

Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates.

The Criegee intermediates, carbonyl oxides proposed by Criegee in 1949 as key intermediates in the ozonolysis of alkenes, play important roles in many aspects of atmospheric chemistry. Because direct detection of these gaseous intermediates was unavailable until recently, previous understanding of their reactions, derived from indirect experimental evidence, had great uncertainties. Recent laboratory detection of the simplest Criegee intermediate CH2OO and some larger members, produced from ultraviolet irradiation of corresponding diiodoalkanes in O2, with various methods such as photoionization, ultraviolet absorption, infrared absorption, and microwave spectroscopy opens a new door to improved understanding of the roles of these Criegee intermediates.

Communication: photodissociation of CH3CHO at 308 nm: observation of H-roaming, CH3-roaming, and transition state pathways together along the ground state surface.

Following photodissociation of acetaldehyde (CH3CHO) at 308 nm, the CO(v = 1-4) fragment is acquired using time-resolved Fourier-transform infrared emission spectroscopy. The CO(v = 1) rotational distribution shows a bimodal feature; the low- and high-J components result from H-roaming around CH3CO core and CH3-roaming around CHO radical, respectively, in consistency with a recent assignment by Kable and co-workers (Lee et al., Chem.

Photodissociation of CH3CHO at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: verification of roaming and triple fragmentation.

By using time-resolved Fourier-transform infrared emission spectroscopy, the HCO fragment dissociated from acetaldehyde (CH3CHO) at 248 nm is found to partially decompose to H and CO. The fragment yields are enhanced by the Ar addition that facilitates the collision-induced internal conversion. The channels to CH2CO + H2 and CH3CO + H are not detected significantly.

How antiferromagnetism drives the magnetization of a ferromagnetic thin film to align out of plane.

Interfacial moments of an antiferromagnet are known for their prominent effects of induced coercivity enhancement and exchange bias in ferromagnetic-antiferromagnetic exchange-coupled systems. Here we report that the unpinned moments of an antiferromagnetic face-centered-cubic Mn layer can drive the magnetization of an adjacent Fe film perpendicular owing to a formation of intrinsic perpendicular anisotropy. X-ray magnetic circular dichroism and hysteresis loops show establishment of perpendicular magnetization on Fe/Mn bilayers while temperature was decreased.