### Abstract

Analyses of high Rydberg series of HCO converging to the (030) vibrational state of the cation establish rovibrational state-detailed thresholds for HCO^{+}. UV-visible laser double resonance isolates series for assignment. Strongly vertical Rydberg-Rydberg transitions from photoselected N′ = O and N′ = 2 rotational levels of the ∑^{-} Renner-Teller vibronic component of the 3pπ ^{2}Π (030) complex define individual series converging to rotational levels, N^{+} = 1 through 5 and 3 through 5 of the HCO^{+} vibrational states (03^{1}0) and (03^{3}0), respectively. Extrapolation of autoionizing series locates the positions of these rovibrational states to within ±0.01 cm^{-1}. The use of this information combined with precise ionization limits for lower vibrational states determined from earlier Rydberg extrapolations and spectroscopic information available from infrared absorption measurements enables an estimate of the force-field parameters for HCO^{+} bending. These parameters include the harmonic bending frequency, ω_{2} = 842.57 cm^{-1}, the vibrational angular momentum splitting constant, g_{22} = 3.26 cm^{-1}, and the diagonal bending anharmonicity, x_{22} = -2.53 cm^{-1}, separated from the off-diagonal contribution, x_{22}, by reference to ab initio calculations. Results of experiment on the higher vibrationally excited states of HCO^{+} are compared with recent theoretical predictions.

Original language | English (US) |
---|---|

Pages (from-to) | 147-157 |

Number of pages | 11 |

Journal | Journal of Molecular Spectroscopy |

Volume | 199 |

Issue number | 2 |

DOIs | |

State | Published - Feb 2000 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics
- Spectroscopy
- Physical and Theoretical Chemistry

### Cite this

^{+}: Determination of ω

_{2}, x

_{22}, g

_{22}, and B(030).

*Journal of Molecular Spectroscopy*,

*199*(2), 147-157. https://doi.org/10.1006/jmsp.1999.8014

**Experimental Characterization of the Higher Vibrationally Excited States of HCO ^{+} : Determination of ω_{2}, x_{22}, g_{22}, and B(030).** / Foltynowicz, Robert J.; Robinson, Jason D.; Zückerman, Eric J.; Hedderich, Hartmut G.; Grant, Edward R.

Research output: Contribution to journal › Article

^{+}: Determination of ω

_{2}, x

_{22}, g

_{22}, and B(030)',

*Journal of Molecular Spectroscopy*, vol. 199, no. 2, pp. 147-157. https://doi.org/10.1006/jmsp.1999.8014

^{+}: Determination of ω

_{2}, x

_{22}, g

_{22}, and B(030). Journal of Molecular Spectroscopy. 2000 Feb;199(2):147-157. https://doi.org/10.1006/jmsp.1999.8014

}

TY - JOUR

T1 - Experimental Characterization of the Higher Vibrationally Excited States of HCO+

T2 - Determination of ω2, x22, g22, and B(030)

AU - Foltynowicz, Robert J.

AU - Robinson, Jason D.

AU - Zückerman, Eric J.

AU - Hedderich, Hartmut G.

AU - Grant, Edward R.

PY - 2000/2

Y1 - 2000/2

N2 - Analyses of high Rydberg series of HCO converging to the (030) vibrational state of the cation establish rovibrational state-detailed thresholds for HCO+. UV-visible laser double resonance isolates series for assignment. Strongly vertical Rydberg-Rydberg transitions from photoselected N′ = O and N′ = 2 rotational levels of the ∑- Renner-Teller vibronic component of the 3pπ 2Π (030) complex define individual series converging to rotational levels, N+ = 1 through 5 and 3 through 5 of the HCO+ vibrational states (0310) and (0330), respectively. Extrapolation of autoionizing series locates the positions of these rovibrational states to within ±0.01 cm-1. The use of this information combined with precise ionization limits for lower vibrational states determined from earlier Rydberg extrapolations and spectroscopic information available from infrared absorption measurements enables an estimate of the force-field parameters for HCO+ bending. These parameters include the harmonic bending frequency, ω2 = 842.57 cm-1, the vibrational angular momentum splitting constant, g22 = 3.26 cm-1, and the diagonal bending anharmonicity, x22 = -2.53 cm-1, separated from the off-diagonal contribution, x22, by reference to ab initio calculations. Results of experiment on the higher vibrationally excited states of HCO+ are compared with recent theoretical predictions.

AB - Analyses of high Rydberg series of HCO converging to the (030) vibrational state of the cation establish rovibrational state-detailed thresholds for HCO+. UV-visible laser double resonance isolates series for assignment. Strongly vertical Rydberg-Rydberg transitions from photoselected N′ = O and N′ = 2 rotational levels of the ∑- Renner-Teller vibronic component of the 3pπ 2Π (030) complex define individual series converging to rotational levels, N+ = 1 through 5 and 3 through 5 of the HCO+ vibrational states (0310) and (0330), respectively. Extrapolation of autoionizing series locates the positions of these rovibrational states to within ±0.01 cm-1. The use of this information combined with precise ionization limits for lower vibrational states determined from earlier Rydberg extrapolations and spectroscopic information available from infrared absorption measurements enables an estimate of the force-field parameters for HCO+ bending. These parameters include the harmonic bending frequency, ω2 = 842.57 cm-1, the vibrational angular momentum splitting constant, g22 = 3.26 cm-1, and the diagonal bending anharmonicity, x22 = -2.53 cm-1, separated from the off-diagonal contribution, x22, by reference to ab initio calculations. Results of experiment on the higher vibrationally excited states of HCO+ are compared with recent theoretical predictions.

UR - http://www.scopus.com/inward/record.url?scp=0000382086&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000382086&partnerID=8YFLogxK

U2 - 10.1006/jmsp.1999.8014

DO - 10.1006/jmsp.1999.8014

M3 - Article

AN - SCOPUS:0000382086

VL - 199

SP - 147

EP - 157

JO - Journal of Molecular Spectroscopy

JF - Journal of Molecular Spectroscopy

SN - 0022-2852

IS - 2

ER -