Benzene molecular beam studies

F.A. Baiocchi et al., Molecular beam studies of hexafluorobenzene, trifluorobenzene, and benzene complexes of hydrogen fluoride. The rotational spectrum of benzene-hydrogen fluoride. J. Phys. Chem. 87, 2079-2084 (1983)... 

Steed, J. M. Dixon, T. A. Klemperer, W. Molecular beam studies of benzene dima, hexafluorobenzene dimer, andbenzene-hexafluorobenzene, 7. Chem. Phys. 1979,70, 4940-4946. 

J. M. Steed, T. A. Dixon, and W. Klemperer,/. Chem. Phys., 70, 4940 (1979). Molecular Beam Studies of Benzene Dimer, Hexafluorobenzene Dimer, and Benzene-Hexafluorobenzene. 

An elegant molecular-beam study of the photofragmentation of aryl halides and methyl iodide has permitted extraction of excited-state lifetimes from a measured anisotropy parameter which depends upon the lifetime of excited state, the rotational correlation time of the molecule, and the orientation of the electronic transition dipole with respect to the —X bond.38 The lifetimes obtained were methyl iodide 0.07 ps, iodobenzene 0.5 ps, a-iodonaphthalene 0.9 ps, and 4-iodobiphenyl 0.6 ps, from which it was concluded that, whereas methyl iodide dissociates directly, the aryl halides predissociate. A crossed-beam experiment using electron-beam excitation has yielded the results for the Si Tt intersystem-crossing relaxation time in benzene, [sHe]benzene, fluorobenzene, and... 

There are relatively few examples of C-C bond formation on solid surfaces under UHV conditions. There are virtually no examples of catalytic C-C bond formation under such conditions. Perhaps the closest precedent for the present studies on reduced Ti02 can be found in the studies of Lambert et al. on single crystal Pd surfaces. Early UHV studies demonstrated that acetylene could be trimerized to benzene on the Pd(lll) surface in both TPD and modulated molecular beam experiments [9,10]. Subsequent studies by the same group and others [11,12] demonstrated that this reaction could be catalyzed at atmospheric pressure both by palladium single crystals and supported palladium catalysts. While it is not clear that catalysis was achieved in UHV, these and subsequent studies have provided valuable insights into the mechanism of this reaction as catalyzed by metals, including spectroscopic evidence for the hypothesized metallacyclopentadiene intermediates [10,13,14]. 

Studies of the photodissociation dynamics of chlorinated benzene derivatives have been reviewed. Photodissociation of chlorobenzene at 266 nm has been investigated by the crossed laser-molecular beam technique, and a hot molecule mechanism is considered probable. Similar studies have been carried out for bromobenzene and p-bromotoluene, which show that for each of these molecules the dissociation is fast and the transition dipole moment is almost perpendicular to the C-Br bond. In deoxygenated aqueous solutions, 254 nm photolysis of chlorobenzene yields phenol and chloride ions as the main products, along with benzene, phenylphenols and biphenyl.lodo-benzene adsorbed on sapphire(OOOl) at 110 K undergoes C-I bond cleavage when irradiated at 193 nm. ... 

In this chapter, we have shown how the recent advances in the crossed molecular beam technique allow us to study complex polyatomic reactions of relevance in astrochemistry. The focus was on the CN radical reactions with simple alkynes, but the same approach has been also applied to the study of other CN radical reactions with unsaturated small organic molecules, such as ethylene, benzene, and allene, which are of relevance in astrochemistry as well [77,81,84]. 

Two recent papers [1,2] provide updated views of advances in the production of intense and continuous beams of aligned molecules. In [1], it was demonstrated that in the prototypical case of a seeded supersonic expansion of a molecular beam of benzene, besides acceleration and cooling, orientation of the molecular plane also occurs because of the anisotropy of the intermolecular forces which govern collisions. This work is reviewed in Sec.2.1. Previous studies on the collisional alignment of the rotational... 

Materials. The nearly monodisperse atactic PMMA, which was used for the electron beam lithography and fluorescence spectroscopy studies, was obtained from Pressure Chemical. It has a weight average molecular weight (Mw) of 188,100 and Mw/Mn< 1.08. Pyrenedodecanoic acid (PDA) used in the fluorescence studies was obtained from Molecular Probes and used as supplied. Spectroscopic grade benzene purchased from J.T. Baker was used as the spreading solvent in the PMMA and PMMA/PDA solutions. 

There are the further advantages that rotational lines can be studied and that fluorescent substances can be investigated by the inverse Raman effect. Benzene and other molecular liquids have been studied by this method by McQuillan and Stoicheff 232) jhe required continuum radiation was anti-Stokes emission produced by passing the laser beam in liquid toluene. 

The first optical absorption bands of benzene and pyridine are known to occur near 5 eV. The optical data on 1000 A thick, solution cast, PS and PVP as well as on the model molecules ethyl benzene and 2-ethyl pyridine in the gas phase were recorded on a Cary 14 double beam instrument. The data are therefore limited to >1 u <6 eV by the optics of the instrument. Condensed molecular solid spectra were not necessary since the photoemission studies had already shown that the polymer and condensed molecular spectra were equivalent. Therefore a comparison of gas-phase model-molecule spectra with that of the corresponding polymer spectra was sufficient. 

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