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- W2061597373 abstract "Abstract High-resolution infrared spectroscopy is used to interrogate a series of inter and intramolecular vibrational quantum states in jet-cooled ortho and para H 2 –HCl and H 2 –DCl complexes, which as a result of weak binding and large zero-point effects provide a novel dynamical window into large-amplitude motion in highly quantum mechanical clusters. The fundamental v HCl =1←0 stretch bands of H 2 –HCl/DCl are observed and elucidate dramatic differences in the vibrationally averaged intermolecular alignment of the H 2 subunit, i.e., T-shaped vs. more nearly isotropic for the lowest ortho (Π) and para (Σ) nuclear spin states, respectively. The two internal-rotor states correlating with H 2 ( j =1) in the o -H 2 –HCl complex are observed via fundamental and combination band excitation built on v HCl =1←0. The 8.5 cm −1 internal-rotor splitting between the ground (Π) and excited (Σ) H 2 alignments confirms the T-shaped minimum energy configuration for the intermolecular potential, with the HCl proton donating into the H 2 subunit. At even higher energies for o -H 2 –HCl, a rich but highly perturbed spectrum of combination band transitions is observed due to the strongly Coriolis coupled manifold ((2 j H 2 +1)(2 j HCl +1)=9) of levels correlating with H 2 ( j =1) and HCl( j =1) subunits. Rotational predissociation broadening accompanied by an abrupt cut off in these combination band spectra is observed and used to estimate a dissociation energy window of D 0 =45±2 and 47±2 cm −1 for the v HCl =0 and 1 intramolecular HCl stretching states, respectively, of the o -H 2 –HCl complex." @default.
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- W2061597373 date "1998-12-01" @default.
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- W2061597373 title "Large-amplitude motion in highly quantum clusters: high-resolution infrared absorption studies of jet-cooled H2–HCl and H2–DCl" @default.
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- W2061597373 doi "https://doi.org/10.1016/s0301-0104(98)00359-0" @default.
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