Spectrum and vibrational predissociation of the HF dimer. I. Bound and quasibound states

Vissers, G. W. M.; Groenenboom, Gerrit C.; Avoird, Ad van der

doi:10.1063/1.1577111

Cited by 34 publications

(24 citation statements)

References 56 publications

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“…50 We will therefore apply this approximation also to the HClHCl system. In the golden rule approximation, the linewidth ⌫ of a resonance is given by FIG.…”

Section: ͑5͒mentioning

confidence: 99%

“…To compute the monomer stretch excited states, a three-step diagonalization of the Hamiltonian was used, which is described in our paper on the bound states of the HF dimer. 50 The bound state ͉ b ͘ in the golden rule expression was calculated in a basis with v A ϩv B ϭ1, 2, j A , j B р13, and n р8. The radial scattering wave function was represented on an equally spaced 332-point grid, in the range (3 -21)a 0 .…”

Section: Computational Detailsmentioning

confidence: 99%

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Vibrational predissociation in the HCl dimer

Vissers

Oudejans

Miller

et al. 2004

The Journal of Chemical Physics

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We present results of a combined theoretical and experimental study on the vibrational predissociation of the HCl dimer. On the theoretical side, photodissociation linewidths and product-state distributions for monomer stretch excited states with total angular momentum Jϭ0 were computed, using the Fermi golden rule approximation. The resonances investigated include excitation of the hydrogen bond donor and acceptor stretches, as well as combinations of one of these modes with the intermolecular stretch and geared bend modes, for both even and odd permutation symmetry. Line strengths for the transitions from the Jϭ1, Kϭ0 ground state to excited states with Jϭ0 were computed using quasibound states. On the experimental side, the photofragment angular distribution method was employed to obtain complete final-state distributions for the monomer stretch excited states. Three different transitions were probed, all starting from the lower tunneling component of the ground state: the R Q 0 (1) transition for excitation of the acceptor stretch and the Q R 0 (0) transition and unresolved R Q 0 branch for the donor stretch excitation. We find that, in contrast to the HF dimer, the excited-state alignment of the HCl dimer, resulting from excitation using a polarized laser beam, is completely lost on the time scale of the dissociation. The agreement between theory and experiment for the product-state distributions and line strengths is reasonable. The computed lifetimes are 1-2 orders of magnitude too small, which is attributed to a deficiency in the potential energy surface.

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“…50 We will therefore apply this approximation also to the HClHCl system. In the golden rule approximation, the linewidth ⌫ of a resonance is given by FIG.…”

Section: ͑5͒mentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Vibrational predissociation in the HCl dimer

Vissers

Oudejans

Miller

et al. 2004

The Journal of Chemical Physics

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“…Since these states are rather longlived, one can approximate them as bound states. This was the approach taken in the preceding paper 1 ͑hereafter called Paper I͒, and for (HF) 2 this results in a set of vibrational frequencies that are in good agreement with experimental data. However, for a better description of the system one should treat the dissociation process.…”

Section: Introductionmentioning

confidence: 51%

“…This is illustrated in Figs. 1 and 2, where the rotational state distribution is plotted for the 1 and 2 resonances of odd permutation symmetry. We see that the 2 distribution is sharply peaked with very strong contributions from the ͑10,2͒, ͑10,4͒, and ͑11,0͒ channels.…”

Section: Resultsmentioning

confidence: 99%

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Spectrum and vibrational predissociation of the HF dimer. II. Photodissociation cross sections and product state distributions

Vissers

Groenenboom

Avoird

2003

The Journal of Chemical Physics

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We study vibrational predissociation of the HF dimer both by a full coupled channels treatment as well as in the Fermi golden rule approximation. Photodissociation cross sections, linewidths, and rotational state distributions are computed for excitations from the ground state with rotational quantum numbers Jϭ1, Kϭ0 to monomer stretch excited states with JϭKϭ0, both for even and odd permutation symmetry. The resonances investigated include excitation of the hydrogen bond donor and acceptor stretches, as well as combinations of one of these modes with the dimer stretch and dimer geared-bending modes. We find that dissociation is sufficiently slow for the Fermi golden rule approximation to be valid. The resonance positions and line strengths are compared with quasibound state calculations. The agreement with experimental data is fairly good for the photofragment angular distributions that were determined from the rotational state distributions, less good for some of the linewidths. Since we carefully checked that the results are converged with respect to the number of vibrational and rotational channels included, the remaining discrepancies are almost certainly due to small deficiencies in the SO-3 potential used in the calculations.

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Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)₂Cluster

Hippler

Oeltjen

Qüack

2023

Israel Journal of Chemistry

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Rovibrationally resolved spectra of the Nj=22, Ka=0←1 transition and of the Nj=23, Ka=0←0 and Ka=1←0 transitions of the hydrogen‐bonded (HF)2 have been measured in the near infrared range near 1.3 μm by cw‐diode laser cavity ring‐down spectroscopy in a pulsed supersonic slit jet expansion. The spectroscopic assignment and analysis provided an insight into the dynamics of these highly‐excited vibrational states, in particular concerning the predissociation of the hydrogen bond and the tunneling process of the hydrogen bond switching. Together with our previously analyzed spectra of the Nj=21 and Nj=22 components, the mode‐specific dynamics in all three components of this triad can now be compared. In the N=2 triad, the HF‐stretching vibration is excited by two quanta with similar excitation energy, but the quanta are distributed in three different ways, which has a distinct influence on the dynamics. The observed band centers and tunneling splittings are in agreement with our recent calculations on the (HF)2 potential energy hypersurface SO‐3, resolving the long‐standing discussion about the symmetry ordering of polyad levels in this overtone region. The results are also discussed in relation to the general questions of non‐statistical reaction dynamics of polyatomic molecules and clusters and in relation to quasi‐adiabatic channel above barrier tunneling.

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Spectrum and vibrational predissociation of the HF dimer. I. Bound and quasibound states

Cited by 34 publications

References 56 publications

Vibrational predissociation in the HCl dimer

Vibrational predissociation in the HCl dimer

Spectrum and vibrational predissociation of the HF dimer. II. Photodissociation cross sections and product state distributions

Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)₂Cluster

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Spectrum and vibrational predissociation of the HF dimer. I. Bound and quasibound states

Cited by 34 publications

References 56 publications

Vibrational predissociation in the HCl dimer

Vibrational predissociation in the HCl dimer

Spectrum and vibrational predissociation of the HF dimer. II. Photodissociation cross sections and product state distributions

Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)2Cluster

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Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)₂Cluster