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Title: 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{sup +} = 0, N{sup +} = 0–2) levels of the X{sup +2}Σ{sub g}{sup +} electronic ground state of HD{sup +} were studied by high-resolution spectroscopy from the GK{sup 1}Σ{sub g}{sup +} (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 30d2{sub 1} and 31g2{sub 2} Rydberg states of gerade symmetry were observed after careful compensation of the stray electric fields. (ii) The singlet 61p1{sub 2} Rydberg state of ungerade symmetry was found to autoionize to the N{sup +} = 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 np1{sub 1} Rydberg series which lie close to nd2{sub 1} 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{sub pd} of singlet-π symmetry was determined to be 0.0023(3) and the corresponding autoionization dynamics could be characterized. The ionization energymore » of the GK (v = 1, N = 1) state of HD was determined to be 12 710.544 23(10) cm{sup −1}.« less
Authors:
;  [1]
  1. Laboratorium für Physikalische Chemie, ETH-Zürich, 8093 Zürich (Switzerland)
Publication Date:
OSTI Identifier:
22253371
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 12; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; AUTOIONIZATION; ELECTRIC FIELDS; GROUND STATES; MIXING; QUANTUM MECHANICS; RYDBERG STATES; SPECTROSCOPY; SYMMETRY BREAKING