On the spin-orbit splitting of CuCl2 in its 2 Pi g ground state

The spin-orbit splitting of CuCl(2) in its ground X(2)Pi(g) state remains an unknown or, at best, poorly defined quantity. The electronic spectrum of CuCl(2) has been studied by Fourier transform resolved, laser-induced fluorescence between 602 and 587 nm, in an attempt to identify transitions to the upper spin component of the ground state. In order to provide a well-defined excitation process, the sample was cooled to rotational temperatures of about 10 K in a free-jet expansion. Observations from just two rotationally perturbed levels in the upper electronic state, one for (63)Cu(35)Cl(2) and the other for (65)Cu(35)Cl(37)Cl, have revealed an additional feature about 482 cm(-1) above the (2)Pi(3/2) state. The effective rotational constants associated with these levels (0.066 20 cm(-1) for (63)Cu(35)Cl(2)) are significantly larger than those for the ground (2)Pi(3/2) state (0.058 13 cm(-1)). Analysis of this feature as the (2)Pi(1/2) component leads to a value of -482.9 cm(-1) for the spin-orbit coupling constant A and of -0.0846 cm(-1) for the lambda-doubling parameter (p+2q) for (63)Cu(35)Cl(2). Several other previously unobserved levels are also identified within 2000 cm(-1) of the ground state. Many of these also have anomalously large rotational constants.