Zakya H. Kafafi

Matrix isolation studies of the reactions of silicon atoms with molecular hydrogen. The infrared spectrum of silylene

Silicon spontaneously inserts into the H–H bond of molecular hydrogen to form silylene in solid argon at 10 K. Infrared frequencies for the three fundamental modes of SiH2, SiHD, and SiD2 have been measured. The band assignments in the present study are totally different from those reported from a previous vacuum‐ultraviolet photolysis study of SiH4. Silylene, formed from the molecular hydrogen reaction with silicon, reacts further with a second hydrogen molecule to give SiH4. The force field of SiH2 has been determined through normal coordinate analysis. Thermodynamic functions have also been calculated for this triatomic molecule.

A Multisurface Matrix-Isolation Apparatus

A multisurface matrix-isolation apparatus has been designed and interfaced to an FT-IR vacuum spectrometer. The design permits independent matrix-isolation studies with sixty different surfaces. It also allows direct measurement of matrix gas to guest ratios with an integral cooled quartz crystal microbalance. Problems associated with moving the matrix block while maintaining good thermal contact are discussed. Finally, some applications to studies of coal pyrolysis, metal atom chemistry, and quantitative analysis are presented.

Activation of O–H and C–O bonds of methanol by photoexcited iron atoms

The activation of the O–H and C–O bonds of methanol has accomplished by photoexcitation of the Fe(MeOH) adduct, formed the cocondensation of iron-methanol with excess of argon at 14K, in the violet (400 nm < λ < 500 nm) and u.v.(280 nm < λ < 360 nm) regions, respectively; prolonged u.v. photolysis leads to the formation of carbon monoxide and hydrogen, an interesting observation in that it apparently represents the reverse of the Fischer–Tropsch process for methanol synthesis.

AB initio calculations and matrix ftir studies of the sulfur trioxide radical anion

Abstract The structures and vibrational frequencies of SO − 3 (C 3v ) and SO − 2 (C 2v ) have been calculated at the UHF SCF/3-21 + G ∗ level. By cocondensation of Cs atoms and SO 3 in an Ar matrix the FTIR spectrum of Cs 4 SO 3 has been measured. The molecule is proposed to have C s symmetry with SO 3 binding to Cs in a bidentate fashion.

The isolation and characterization of copper methylene via matrix isolation spectroscopy

Abstract The reactions of copper atoms with diazomethane have been investigated via FTIR matrix isolation spectroscopy. In argon matrices CuCH 2 and N 2 CuCH 2 have been characterized whereas only N 2 CuCH 2 is observed in nitrogen matrices.

Activation of ethane, propane, and cyclopropane by photoexcited iron atoms

Monoatomic iron undergoes photoinsertion into the carbon–hydrogen bonds of ethane and n-propane and into the carbon–carbon bond of cyclopropane.

Isolation and characterization of ZnCH2 by Fourier transform I.R. matrix isolation spectroscopy and its photolytic rearrangement to HZnCH

The 1 : 1 adduct produced by cocondensing monoatomic zinc, diazomethane and argon onto a cold surface at 12 K can be converted to ZnCH2 with λ400 nm photolysis; a carbene→carbyne rearrangement of ZnCH2 to HZnCH is observed during u.v. photolysis.