Observation of g/u-symmetry mixing in the high-n Rydberg states of HD.

The structure and dynamics of high-n Rydberg states belonging to series converging to the (v(+) = 0, N(+) = 0-2) levels of the X(+) (2)Σ(g)(+)electronic ground state of HD(+) were studied by high-resolution spectroscopy from the GK (1)Σ(g)(+) (v = 1, N = 1) state under field-free conditions. Three effects of g/u-symmetry breaking were detected: (i) Single-photon transitions from the GK (v = 1, N = 1) state of gerade symmetry to the 30d21 and 31g22 Rydberg states of gerade symmetry were observed after careful compensation of the stray electric fields. (ii) The singlet 61p12 Rydberg state of ungerade symmetry was found to autoionize to the N(+) = 0, ℓ = 2 ionization continuum of gerade symmetry with a lifetime of 77(10) ns. (iii) Shifts of up to 20 MHz induced by g/u-symmetry mixing were measured for members of the np11 Rydberg series which lie close to nd21 Rydberg states. These observations were analyzed in the framework of multichannel quantum-defect theory. From the observed level shifts, the off-diagonal eigenquantum-defect element μ(pd) of singlet-π symmetry was determined to be 0.0023(3) and the corresponding autoionization dynamics could be characterized. The ionization energy of the GK (v = 1, N = 1) state of HD was determined to be 12 710.544 23(10) cm(-1).