Journal of Physical Chemistry A, Vol.111, No.49, 12629-12634, 2007
In situ photolysis of CD3I in solid orthodeuterium
Photochemical reactions of molecules in solid orthodeuterium (o-D-2) have been studied by high-resolution infrared spectroscopy and compared with previous results obtained in solid parahydrogen (p-H-2). Ultraviolet photoplysis of CD3I molecules in solid o-D2 yielded CD3 radicals and iodine atoms efficiently, which indicates a small cage effect in solid o-D2, as in the case of solid p-H2. The Fourier transform infrared spectrum of the nu(3) vibrational band of CD3 showed a rotational structure with additional splitting due to crystal field interactions. The magnetic dipole transition (2P(1/2) (<-) P-2(3/2)) of the I atom isolated in solid o-D-2 was observed together with a strong rotational satellite of deuterium molecules through the electron-roton coupling in solid hydrogen. The tunneling reaction between CD3 and D-2 was not observed in a time scale of a few days, which gives the upper limit of the tunneling,reaction rate of 10(-8) s(-1) at 4.2 K.