Vibrational predissociation in the HCl dimer

Vissers, G. W. M.; Oudejans, L.; Miller, R. E.; Groenenboom, Gerrit C.; Avoird, Ad van der

doi:10.1063/1.1711601

Cited by 23 publications

(17 citation statements)

References 59 publications

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“…Interaction of this quadrupole with the quadrupole of Cl( 2 P) leads to maximum binding for a T-shaped Cl-HCl complex. Similar T-shaped equilibrium structures were found for OH-HCl, 23 HCl-HCl, 24 and HCN-HCl. 25 For F-HF three minima were found, 26 one for each of the two linear geometries and a T-shaped one.…”

Section: Resultssupporting

confidence: 77%

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(²P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

2007

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The three adiabatic potential surfaces of the Br( 2 P)-HCN complex that correlate to the 2 P ground state of the Br atom were calculated ab initio. With the aid of a geometry-dependent diabatic mixing angle, also calculated ab initio, these adiabatic potential surfaces were transformed into a set of four diabatic potential surfaces required to define the full 3 × 3 matrix of diabatic potentials. Each of these diabatic potential surfaces was expanded in terms of the appropriate spherical harmonics in the atom-linear molecule Jacobi angle θ. The dependence of the expansion coefficients on the distance R between Br and the HCN center of mass and on the CH bond length was fit to an analytic form. For HCN in its equilibrium geometry, the global minimum with D e ) 800.4 cm -1 and R e ) 6.908a 0 corresponds to a linear Br-NCH geometry, with an electronic ground state of Σ symmetry. A local minimum with D e ) 415.1 cm -1 , R e ) 8.730a 0 , and a twofold degenerate Π ground state is found for the linear Br-HCN geometry. The binding energy, D e , depends strongly on the CH bond length for the Br-HCN complex and much less strongly for the Br-NCH complex, with a longer CH bond giving stronger binding for both complexes. Spin-orbit coupling was included and diabatic states were constructed that correlate to the ground 2 P 3/2 and excited 2 P 1/2 spin-orbit states of the Br atom. For the ground spin-orbit state with electronic angular momentum j ) ( 3 / 2 ) the minimum in the potential for projection quantum number ω ) (( 3 / 2 ) coincides with the local minimum for linear Br-HCN of the spin-free case. The minimum in the potential for projection quantum number ω ) (( 1 / 2 ) occurs for linear Br-NCH but is considerably less deep than the global minimum of the spin-free case. According to the lowest spin-orbit coupling included adiabatic potential the two linear isomers, Br-NCH and Br-HCN, are about equally stable. In the subsequent paper, we use these potentials in calculations of the rovibronic states of the Br-HCN complex.

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Section: Resultssupporting

confidence: 77%

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(²P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

2007

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“…See, for example, work on HF-HF ͑Refs. 23 and 24͒ and HCl-HCl, 25 as well as on the water dimer. 26,27 In all these hydrogen bonded complexes there is a tunneling process that interchanges the donor and the acceptor in the hydrogen bond.…”

Section: Introductionmentioning

confidence: 92%

Isotope effects in the CO dimer: Millimeter wave spectrum and rovibrational calculations of (C12O18)2

Surin¹,

Fourzikov²,

Giesen³

et al. 2006

The Journal of Chemical Physics

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The millimeter wave spectrum of the isotopically substituted CO dimer, (12C18O)2, was studied with the Orotron jet spectrometer, confirming and extending a previous infrared study [A. R. W. McKellar, J. Mol. Spectrosc. 226, 190 (2004)]. A very dilute gas mixture of CO in Ne was used, which resulted in small consumption of 12C18O sample gas and produced cold and simple spectra. Using the technique of combination differences together with the data from the infrared work, six transitions in the 84-127 GHz region have been assigned. They belong to two branches, which connect four low levels of A+ symmetry to three previously unknown levels of A- symmetry. The discovery of the lowest state of A- symmetry, which corresponds to the projection K=0 of the total angular momentum J onto the intermolecular axis, identifies the geared bending mode of the 12C18O dimer at 3.607 cm(-1). Accompanying rovibrational calculations using a recently developed hybrid potential from ab initio coupled cluster [CCSD(T)] and symmetry-adapted perturbation theory calculations [G. W. M. Vissers et al., J. Chem. Phys. 122, 054306 (2005)] gave very good agreement with experiment. The isotopic dependence of the A+/A- energy splitting, the intermolecular separation R, and the energy difference of two ground state isomers, which change significantly when 18O or 13C are substituted into the normal (12C16O)2 isotopolog [L. A. Surin et al., J. Mol. Spectrosc. 223, 132 (2004)], was explained by these calculations. It turns out that the change in anisotropy of the intermolecular potential with respect to the shifted monomer centers of mass is particularly significant.

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“…Detailed spectroscopic and theoretical studies of important prototypes of the hydrogen bonding such as the HF, HCl and H 2 O homodimers have led to the determination of accurate ab initio full potential energy surfaces devoted to weak intermolecular interactions. [1][2][3][4] The investigation of dimers formed from two different small monomers causes more experimental difficulties, particularly because of the possible competition between the formation of heterodimers and homodimers of comparable binding energy.…”

Section: Introductionmentioning

confidence: 99%

Fourier transform infrared spectroscopy and ab initio theory of acid–hydrogen sulfide clusters: H₂S–HCl, D₂S–DCl and H₂S–(HCl)₂

Asselin

Soulard

Madebène

et al. 2007

Phys. Chem. Chem. Phys.

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The rotationally resolved Fourier transform infrared (FTIR) spectrum of the nu(s) HCl and DCl stretching bands for the hydrogen bonded complex H2S-HCl and its isotopomer D2S-DCl have been observed in a supersonic jet at 0.02 cm(-1) resolution. In the same experimental conditions, two additional bands observed without rotational structure in the HCl range of the dimer have been assigned to the cyclic trimer H2S-(HCl)(2). The multidimensional coupling picture involving the donor stretch mode nu(s) and low frequency intermolecular modes already evidenced in several medium strength hydrogen bonded complexes is beautifully confirmed by the observation of completely separated hot band progressions in the 198 K cell spectrum of both dimers. Based on our anharmonic adiabatic approach for the treatment of the coupled vibrations, absolute vibrational frequencies, diagonal and off-diagonal anharmonicities as well as rovibrational coupling constants obtained from analyses of several 2-D subspaces at MP2 and CCSD(T) level are in excellent agreement with spectroscopic results. In the case of small light complexes, the combination of elevated rotational constants and a negligible contribution of intramolecular vibrational redistribution (IVR) improve the reliability of predissociation lifetime measurements, estimated to 180 ps for H2S-HCl and above 200 ps for D2S-DCl.

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Vibrational predissociation in the HCl dimer

Cited by 23 publications

References 59 publications

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(²P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(²P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

Isotope effects in the CO dimer: Millimeter wave spectrum and rovibrational calculations of (C12O18)2

Fourier transform infrared spectroscopy and ab initio theory of acid–hydrogen sulfide clusters: H₂S–HCl, D₂S–DCl and H₂S–(HCl)₂

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Vibrational predissociation in the HCl dimer

Cited by 23 publications

References 59 publications

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(2P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(2P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

Isotope effects in the CO dimer: Millimeter wave spectrum and rovibrational calculations of (C12O18)2

Fourier transform infrared spectroscopy and ab initio theory of acid–hydrogen sulfide clusters: H2S–HCl, D2S–DCl and H2S–(HCl)2

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Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(²P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(²P)−HCN. 1. Adiabatic and Diabatic Potential Surfaces

Fourier transform infrared spectroscopy and ab initio theory of acid–hydrogen sulfide clusters: H₂S–HCl, D₂S–DCl and H₂S–(HCl)₂