The structure and ground state dynamics of Ar–IH

Abstract

Effect of solvent on molecular conformation: Microwave spectra and structures of 2-aminoethanol van der Waals complexesAb initio relativistic all-electron calculation of the Ar-I 2 ground state potential A study of the ArCl 2 Van der Waals complex: Ab initio-based potential energy surfaces, the relative stability of conformers, and the "hidden" microwave spectrumThe structure and ground state dynamics of the atom-diatom dimer interaction between Ar and HI has been investigated by microwave and near infrared supersonic jet spectroscopy. Ab initio molecular orbital calculations were used to provide greater insight into the nature of the interaction. The ground state is shown to be in the isomeric form Ar-IH with R cm ϭ3.9975(1) Å, ϭ149.33(1)°for the normal isotopomer and R cm ϭ3.9483(1) Å, ϭ157.11(1)°for Ar-ID. The potential surface from an ab initio molecular orbital calculation was scaled and shifted to yield a nonlinear least-squares fit of the rovibrational state energies to the experimental data. The ground state potential energy surface obtained in this manner has a barrier between the Ar-IH and Ar-HI isomers of 88.5 cm Ϫ1 with respect to the global minimum. Such calculations are also used to predict the presence of localized states in the secondary minimum associated with isomers Ar-HI and Ar-DI. Attempts to experimentally identify transitions associated with the latter were unsuccessful. The ground state, Ar-IH isomeric structure, contrasts with the corresponding ground state of the other members of the homologous series Ar-HX ͑XϭF, Cl, and Br͒ in which the Ar is bound to the proton.

An energy-resolved study of the partial fragmentation dynamics of Ar–HCl into H+Ar–Cl after ultraviolet photodissociation

“…The system Ar•••I-H seems to be one of such clusters. 19,35,36 In Rg-HX clusters where the hydrogen is in between the heavier atoms in the equilibrium configuration, infrared excitation of vibrational overtones of the HX chromophore prior to the UV excitation could increase the floppiness of the hydrogen bond. 21,37 The amount of energy available for the Rg-X fragment is an additional factor to control and increase the yield of radical formation.…”

Pressure broadening and shifting parameters for the spectral lines in the fundamental vibration–rotation bands of HBr and HI in mixtures with rare gases

“…Considerable progress was made during last decades in the studies of the anisotropic interaction potential energy surfaces for the HHal-Rg van der Waals complexes. Most of the presently developed PES for the HBr-Rg and HI-Rg heterodimers generated in supersonic molecular jets were based on matching the rotationally resolved microwave or IR spectral data [26][27][28][29][30][31][32][33][34]. Some purely ab initio PES were also reported [35,36].…”

Quantum treatment of the Ar-HI photodissociation dynamics

“…The Ar-HI system is the last member of the Ar-HX series of clusters, but to date its photolysis behavior has not been explored theoretically. This cluster presents the special feature that its ground vdW state corresponds to the Ar-I-H isomer, 25,26 while in the other Ar-HX complexes such a state is associated to the Ar-H-X isomer.…”