The photolysis of ethyl iodide in solid parahydrogen leads to the
formation of ethyl radical, ethylene, and
ethane upon near-UV illumination at about 5 K which are characterized
by vibrational spectroscopy. The
mechanism of the formation of the products is elucidated consistently.
Two kinds of ethylene are discriminated
spectroscopically which show distinctly different temporal behaviors
during illumination and standing under
dark. One of them is attributed to a complex between ethylene and
iodine atom. The present work demonstrates
that the cage effect is insignificant in the solid parahydrogen matrix,
and a variety of elementary reactions of
in situ photolysis can be studied in detail in contrast to
conventional rare gas matrices.
The refractive index of water was measured at atmospheric pressure under magnetic fields up to 10 T and found to increase by ∼0.1% with increasing magnetic field strength. In contrast, the refractive index of saturated aqueous electrolyte solutions decreased under the magnetic field. In the case of n-hexane, any change of the optical property by the magnetic field was not found. A possible explanation is that the lifetime of the hydrogen bond is prolonged due to the electron delocalization of a water dimer under the magnetic field.
Ultraviolet photolysis of CD3I in solid parahydrogen at 5 K gives CD3 radical, which decreases in a single exponential manner with a rate constant of (4.7±0.5)×10−6 s−1. Concomitantly, CD3H is formed, which is accounted for by the quantum tunneling reaction CD3+H2→CD3H+H. Under the same conditions, CH3I yields CH3 radical, but the corresponding reaction between CH3 and H2, expected to give CH4+H, does not proceed measurably at 5 K. The difference between the two systems is attributed to the difference in the zero point energy change.
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