Double-resonance spectroscopy of the high Rydberg states of HCO. I. A precise determination of the adiabatic ionization potential
- Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 (United States)
We report the first spectroscopic observation of the high Rydberg states of HCO. Individual lines in a system of vibrationally autoionizing Rydberg series converging to the (010) state of HCO{sup +} are rotationally labeled in a double-resonance excitation scheme that uses resolved levels in the (010) {ital A}{prime} vibronic component of the 3{ital p}{pi} {sup 2}{Pi} Rydberg state as intermediates. Observed high-Rydberg structure extends from the adiabatic ionization threshold---which falls just below the principal quantum number of 12 in the vibrationally excited series---to the (010) vertical threshold. Elements of a single series extending from {ital n}=12 to 50, for which the total angular momentumless spin can be assigned as {ital N}=1, are extrapolated to obtain a vertical convergence limit with respect to the 3{ital p}{pi} {sup 2}{Pi}(010){ital A}{prime} {ital N}{prime}=0 intermediate state of 20 296.9{plus_minus}0.3 cm{sup {minus}1}. Referring this transition energy to the ground state, and subtracting the precisely known fundamental bending frequency of the cation, establishes the adiabatic ionization potential corresponding to the transition from HCO {sup 2}{ital A}{prime}(000) {ital J}{double_prime}=0, {ital K}{double_prime}=0 to HCO{sup +} {ital J}{sup +}=0 {sup 1}{Sigma}{sup +}(000). The result is 65 735.9{plus_minus}0.5 cm{sup {minus}1} or 8.150 22{plus_minus}0.000 06 eV. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.
- DOE Contract Number:
- FG02-93ER14401
- OSTI ID:
- 132856
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 103; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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