High-resolution continuous-wave-diode laser cavity ring-down spectroscopy of the hydrogen fluoride dimer in a pulsed slit jet expansion:: Two components of the N=2 triad near 1.3 μm

The near-infrared overtone spectra of the prototypical hydrogen-bond hydrogen fluoride dimer (HF)(2) contain rich information on hydrogen bond dynamics. We report a study of the N = 2 triad involving excitations with two quanta of HF stretching in (HF)2 around 1.3 mu m (7500-7800 cm(-1)) by means of continuous-wave-diode laser cavity ring-down spectroscopy in a pulsed supersonic slit jet expansion. The analysis of the rotationally resolved overtone spectra allows the study of vibrational mode-selective kinetics, such as hydrogen bond predissociation with lifetimes. tau(PD) and tunneling rearrangement (switching) processes. with periods tau(sw) obtained from the tunneling splitting APT in highly excited vibrational states. The K, = 1 <- 0 transition of the Nj = 22 band of (HF)2 has been reinvestigated by us in a supersonic jet expansion; the much improved data obtained here are in excellent agreement with several previous experimental results. Our analysis provides subband-level positions and properties nu($) over bar0(K-a = I(A(+))) = 7711.37956(66) cm-1, APT = 0.0936(10) cm-1, and tau(PD) = 1.3-1.9 x 10(-9) s, depending on the level symmetry A(+) and B+. We have also analyzed spectra of the Nj = 21 band, which we have observed for the first time in a supersonic jet with rotational resolution. For the Ka = 0 <- 0 transition of this band, we find the band center at PO(A(+)) = 7550.3555(26) cm-1 and a tunneling splitting of APT = 0.0150(37) cm-1. This level involves mostly excitation of the H-bonded HF stretching with two quanta. The mode-selective tunneling switching is in agreement with a simple picture of inhibited tunneling. These experimental values are close to those calculated on the SO-3 potential energy hypersurface of Klopper, Quack, and Suhm. The N = 2 triad also exhibits a strongly mode-selective predissociation dynamics, with a predissociation lifetime tau(PD) = 4.99(84) x 10(-11) s in the Nj = 21 level, which is more than 20 times shorter than that for the Nj = 22 level.