Probing the predissociated levels of the S1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy
Here, we report two new experimental schemes to obtain rotationally resolved high-resolution spectra of predissociated S1 acetylene levels in the 47 000-47 300 cm-1 energy region (~1200 cm-1 above the predissociation threshold). The two new detection schemes are compared to several other detection schemes (employed at similar laser power, molecular beam temperature, and number of signal averages) that have been used in our laboratory to study predissociated S1 acetylene levels, both in terms of the signal-to-noise ratio (S/N) of the resultant spectra and experimental simplicity. In the first method, H-atoms from the predissociated S1 acetylene levels are probed by two-photon laser-induced fluorescence (LIF). The H-atoms are pumped to the 3d level by the two-photon resonance transition at 205.14 nm. The resulting 3d–2p fluorescence (654.5 nm) is collected by a photomultiplier. The S/N of the H-atom fluorescence action spectrum is consistently better by ~3× than that of the more widely used H-atom resonance-enhanced multiphoton ionization (REMPI) detection. Laser alignment is also considerably easier in H-atom fluorescence detection than H-atom REMPI detection due to the larger number-density of molecules that can be used in fluorescence vs. REMPI detection schemes. In the second method, fluorescence from electronically excited C2 and C2H photofragments of S1 acetylene is detected. In contrast to the H-atom detection schemes, the detected C2 and C2H photofragments are produced by the same UV laser as is used for the ÖX acetylene excitation. As a result, laser alignment is greatly simplified for the photofragment fluorescence detection scheme, compared to both H-atom detection schemes. Using the photofragment fluorescence detection method, we are able to obtain action spectra of predissociated S1 acetylene levels with S/N ~2× better than the HCCH REMPI detection and ~10× better than H-atom and HCCH LIF detection schemes.
- Research Organization:
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
- Grant/Contract Number:
- FG02-87ER13671
- OSTI ID:
- 1597424
- Alternate ID(s):
- OSTI ID: 1733357; OSTI ID: 1831795
- Journal Information:
- Journal of Chemical Physics, Vol. 149, Issue 17; ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
One-colour (∼220 nm) resonance-enhanced (S 1 − S 0 ) multi-photon dissociation of acetylene: probe of the C 2 A 1 Π u − X 1 Σ + g band by frequency-modulation spectroscopy
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journal | February 2020 |
Determination of the sign of the population difference in a two-level system by frequency-modulation spectroscopy
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journal | August 2019 |
Photoinduced C–H bond fission in prototypical organic molecules and radicals
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journal | January 2019 |
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