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Determination of the binding energies of the np
Rydberg states of H2
, HD, and D2
from high-resolution spectroscopic data by multichannel quantum-defect theory
5. J. Liu, E. J. Salumbides, U. Hollenstein, J. C. J. Koelemeij, K. S. E. Eikema, W. Ubachs, and F. Merkt, J. Chem. Phys. 130, 174306 (2009).
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25. H. M. Crosswhite, The Hydrogen Molecule Wavelength Tables of Gerhard Heinrich Dieke (Wiley-Interscience, New York, 1972).
See supplementary material at http://dx.doi.org/10.1063/1.4866809
for numerical values of the specific mass correction, the final adjusted eigenquantum-defect parameters, and tables containing experimental term values of 781 low-np
states of H2
from the literature and their comparison to MQDT calculations. [Supplementary Material]
42. Ch. Jungen, “Elements of quantum defect theory,” in Handbook of High-resolution Spectroscopy, edited by M. Quack and F. Merkt (John Wiley & Sons, Ltd., 2011).
44. R. N. Zare, Angular Momentum (John Wiley & Sons, New York, 1988).
56. H. Lefebvre-Brion and R. W. Field, The Spectra and Dynamics of Diatomic Molecules (Elsevier, Amsterdam, 2004).
63. D. Sprecher and F. Merkt, “Observation of g/u-symmetry mixing in the high-n Rydberg states of HD,” J. Chem. Phys. (to be published).
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Multichannel quantum-defect theory (MQDT) is used to calculate the electron binding energies of np Rydberg states of H2, HD, and D2 around n = 60 at an accuracy of better than 0.5 MHz. The theory includes the effects of rovibronic channel interactions and the hyperfine structure, and has been extended to the calculation of the asymmetric hyperfine structure of Rydberg states of a heteronuclear diatomic molecule (HD). Starting values for the eigenquantum-defect parameters of MQDT were extracted from ab initio potential-energy functions for the low-lying p Rydberg states of molecular hydrogen and subsequently refined in a global weighted fit to available experimental data on the singlet and triplet Rydberg states of H2 and D2. The electron binding energies of high-np Rydberg states derived in this work represent important quantities for future determinations of the adiabatic ionization energies of H2, HD, and D2 at sub-MHz accuracy.
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