Precision measurement of light shifts in a single trapped Ba^+ ion

Using a single trapped barium ion we have developed an rf spectroscopy technique to measure the ratio of the off-resonant vector ac Stark effect (or light shift) in the 6S_{1/2} and 5D_{3/2} states to 0.1% precision. We find R = Delta_S / Delta_D = -11.494(13) at 514.531 nm where Delta_{S,D} are the light shifts of the m = +/- 1/2 splittings due to circularly polarized light. Comparison of this result with an ab initio calculation of R would yield a new test of atomic theory. By appropriately choosing an off-resonant light shift wavelength one can emphasize the contribution of one or a few dipole matrix elements and precisely determine their values.