Second-order density functional calculations of the MgFH potential energy surface

Sanz, Virgilio; Aguado, Alfredo; Paniagua, Miguel

doi:10.1016/s0166-1280(97)00317-5

Cited by 4 publications

(1 citation statement)

References 45 publications

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“…This model predicts a rather shallow HCaCl insertion well. This well is, however, much deeper in other related systems such as Ca-HF, 35 Mg-HF, 36 Sr-HF, 37 and Be-HF. 38 It is assumed that the well is artificially shallow in the DIM model because the contribution of the H − Ca 2+ Cl − configuration, among others, is not considered.…”

Section: Introductionmentioning

confidence: 89%

Ab initio potential-energy surface for the reaction Ca+HCl→CaCl+H

Verbockhaven

Sanz-Sanz

Groenenboom

et al. 2005

The Journal of Chemical Physics

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The potential-energy surface of the ground electronic state of CaHCl has been obtained from 6400 ab initio points calculated at the multireference configuration-interaction level and represented by a global analytical fit. The Ca+ HCl→ CaCl+ H reaction is endothermic by 5100 cm −1 with a barrier of 4470 cm −1 at bent geometry, taking the zero energy in the Ca+ HCl asymptote. On both sides of this barrier are potential wells at linear geometries, a shallow one due to van der Waals interactions in the entrance channel, and a deep one attributed to the H − Ca ++ Cl − ionic configuration. The accuracy of the van der Waals well depth, Ϸ200 cm −1 , was checked by means of additional calculations at the coupled-cluster singles and doubles with perturbative triples level and it was concluded that previous empirical estimates are unrealistic. Also, the electric dipole function was calculated, analytically fitted in the regions of the two wells, and used to analyze the charge shifts along the reaction path. In the insertion well, 16 800 cm −1 deep, the electric dipole function confirmed the ionic structure of the HCaCl complex and served to estimate effective atomic charges. Finally, bound rovibrational levels were computed both in the van der Waals well and in the insertion well, and the infrared-absorption spectrum of the insertion complex was simulated in order to facilitate its detection.

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Section: Introductionmentioning

confidence: 89%

Ab initio potential-energy surface for the reaction Ca+HCl→CaCl+H

Verbockhaven

Sanz-Sanz

Groenenboom

et al. 2005

The Journal of Chemical Physics

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Mechanism of the collision energy and reagent vibration’s effects on the collision time for the reaction Ca+HCl

Chao

Han

et al. 2015

Computational and Theoretical Chemistry

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High-resolution infrared spectroscopy of Mg–HF and Mg–(HF)2 solvated in helium nanodroplets

Stiles

Douberly

Miller

2009

The Journal of Chemical Physics

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High-resolution infrared (IR) spectroscopy is used to investigate the Mg-HF and Mg-(HF)(2) van der Waals complexes. Both complexes are formed and probed within helium nanodroplets. Rotationally resolved zero-field and Stark spectra are assigned to a linear binary complex composed of a Mg atom bound to the hydrogen end of the HF molecule. Although high level ab initio calculations predict a fluorine bonded complex, none of the observed IR bands can be assigned to this complex. The collocation method is employed to determine the bound states on the two-dimensional intermolecular Mg-HF potential energy surface. The ground and first excited state wave functions for this potential surface have zero amplitude in the well corresponding to the fluorine bonded complex, consistent with experiment. The two HF stretching bands of the Mg-(HF)(2) complex are observed and assigned using a combination of the spectral symmetry, ab initio calculations, pick-up cell pressure dependencies, and dipole moment measurements. Comparisons with the helium solvated HF dimer show large changes to the HF stretching frequencies upon the addition of a single Mg atom to the hydrogen side of (HF)(2).

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Second-order density functional calculations of the MgFH potential energy surface

Cited by 4 publications

References 45 publications

Ab initio potential-energy surface for the reaction Ca+HCl→CaCl+H

Ab initio potential-energy surface for the reaction Ca+HCl→CaCl+H

Mechanism of the collision energy and reagent vibration’s effects on the collision time for the reaction Ca+HCl

High-resolution infrared spectroscopy of Mg–HF and Mg–(HF)2 solvated in helium nanodroplets

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