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American Institute of Physics, The Journal of Chemical Physics, 24(144), p. 244201

DOI: 10.1063/1.4954159

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Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

Journal article published in 2016 by J. Karhu ORCID, J. Nauta ORCID, M. Vainio, M. Metsälä, S. Hoekstra ORCID, L. Halonen
This paper is available in a repository.
This paper is available in a repository.

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Abstract

A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, $ν_1+ν_2+ν_3+ν_4^1+ν_5^{-1}$ in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) $\text{cm}^{-1}$, the rotational parameter $B$ was 1.162222 $\text{cm}^{-1}$, and the quartic centrifugal distortion parameter $D$ was 3.998(62)$\times 10^{-6} \text{cm}^{-1}$, where the numbers in the parenthesis are one-standard errors in the least significant digits.