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INTRAMOLECULAR DYNAMICS OF THE $N = 2$ HF STRETCHING OVERTONE POLYAD OF $(HF)_{2}$ STUDIED BY HIGH-RESOLUTION cw-DIODE LASER CAVITY RING-DOWN SPECTROSCOPY IN A PULSED SLIT JET

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/20336

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Title: INTRAMOLECULAR DYNAMICS OF THE $N = 2$ HF STRETCHING OVERTONE POLYAD OF $(HF)_{2}$ STUDIED BY HIGH-RESOLUTION cw-DIODE LASER CAVITY RING-DOWN SPECTROSCOPY IN A PULSED SLIT JET
Creators: Hippler, Michael; Oeltjen, Lars; Quack, Martin
Issue Date: 2002
Abstract: The $(HF)_{2}$ hydrogen bonded dimer has been a prototype system for high-resolution spectroscopy since the pioneering studies of its microwave spectra by Dyke, Howard, and Klemperer in $1972.^{1}$ Subsequently the HF stretching fundamentals were studied in $1983,^{2}$ a low frequency fundamental analyzed in the far infrared in $1987,^{3}$ HF stretching overtone spectra investigated by FTIR $spectroscopy^{4}$ and finally full dimensional potential energy hypersurfaces developed of near to spectroscopic $accuracy.^{5,6}$ All these were ``first'' achievements prototypical for any type of hydrogen bonded dimer of this kind. Here we present the first study of the $N = 2$ HF stretching overtone polyad by very high resolution cw-diode laser cavity ring-down spectroscopy in pulsed slit jet expansions developed $recently^{7}$ (instrumental bandwidth about 1 MHz corresponding to a resolving power of $2 \times 10^{8}$). An analysis of all polyad subbands in terms of spectroscopic constants, tunneling splittings, Lorentzian predissociation and Doppler contributions to the linewidths will be $presented.^{8}$ The results agree well with full six-dimensional $calculations^{9}$ but disagree with simple models or approximate calculations that have been presented in the past.
URI: http://hdl.handle.net/1811/20336
Other Identifiers: 2002-FA-08
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