The hyperfine coupling constant A of a hydrogen isotope confined in a cage
differs from its vacuum value, demonstrating that the atom acts as a probe
of its environment. Room-temperature values of A for muonium in different c
ube-shaped Si8O12 units (T-8 units or octasilsesquioxanes), in H2O, and in
D2O were determined with an accuracy of about 1 MHz. The results are compar
ed with those obtained from high-resolution ESR on H in H2O, and D in D2O,
and in different silsesquioxanes in the temperature range 40-300 K. Both th
e strong isotope effect and the temperature dependence are well described b
y a single-oscillator model of Roduner et al. (J. Chem. Phys. 102 (1995) 59
89). Striking differences seen between the different silsesquioxanes and be
tween the porous Optipur and bulk Suprasil reflect varying spatial constrai
nts and electronic interactions. (C) 2000 Elsevier Science B.V. All rights
reserved.