Representing Born -Oppenheimer breakdown radial correction functions for diatomic molecules

@article{Roy2002RepresentingB,
  title={Representing Born -Oppenheimer breakdown radial correction functions for diatomic molecules},
  author={R. L. Roy and Yiye Huang},
  journal={Journal of Molecular Structure-theochem},
  year={2002},
  volume={591},
  pages={175-187}
}
Abstract The empirical determination of Born–Oppenheimer breakdown (BOB) correction functions from the analysis of high resolution diatomic molecule spectra is becoming increasingly common. However, in virtually all applications to date, the analytic expressions used to represent those functions have unphysical limiting behaviour which makes the resulting overall potential energy functions unusable at long-range. This paper delineates the limiting physical constraints, which should be imposed… Expand

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References

SHOWING 1-10 OF 66 REFERENCES
Born-Oppenheimer breakdown effects in the determination of diatomic internuclear potentials: Application of a least-squares fitting procedure to the HCl molecule
Abstract This paper describes a least-squares fitting procedure for the reduction of measured line positions in 1Σ diatomic spectra to effective internuclear potentials. The procedure, which is basedExpand
Isotopic dependence of Born-Oppenheimer breakdown effects in diatomic hydrides: The X1Σ+ states of and
Abstract Line positions available from literature data for HI DI and HBr DBr have been employed to determine corrections to the Born-Oppenheimer approximation. For the ground X1Σ+ states of HI andExpand
Experimental Born-Oppenheimer Potential for the X1Sigma+ Ground State of HeH+: Comparison with the Ab Initio Potential.
TLDR
The fitted potential and Born-Oppenheimer breakdown functions are shown to be in good agreement with the results of ab initio calculations and are used to obtain high-order centrifugal distortion constants as well as level widths for quasi-bound levels. Expand
Determination of diatomic molecular constants using an inverted perturbation approach: Application to the A1Σu+-X1Σg+ system of Mg2
Abstract The measurements of the A 1 Σ u + -X 1 Σ g + system of the Mg2 molecule of Balfour and Douglas have been reevaluated and molecular constants have been determined using a variationalExpand
Direct potential fit analysis of the X 1Σg+ state of Rb2: Nothing else will do!
High resolution A-X emission data involving vibrational levels of the ground X 1Σg+ electronic state up to v″=113, spanning 99.8% of the potential well, have been acquired for three isotopomers ofExpand
A “modified Lennard-Jones oscillator” model for diatom potential functions
A flexible new analytical representation for the internuclear potential energy of a diatomic molecule is proposed and tested. The new model may be thought of as a generalization of the prototypicalExpand
Reduction of spectra to parameters of an effective diatomic Hamiltonian containing the generalized potential-energy function with correct long-range part. Application to ArH+ in the ground electronic state
Abstract Infrared and microwave spectra of ArH+ spanning more than half the potential well depth (in total 331 lines belonging to six isotopomers) are reduced to parameters of an effectiveExpand
The Radial Hamiltonians for the X1Σ+ and B1Σ+ States of HCl
Abstract All literature vibration–rotational and pure rotational transition energies for the ground X1Σ+ electronic state of H35Cl, H37Cl, D35Cl, and D37Cl, along with the entire collection ofExpand
Born–Oppenheimer Breakdown Effects from Rotational Analysis of theA1Σ+–X1Σ+Band System of BeH+, BeD+, and BeT+
Abstract The A 1 Σ + –X 1 Σ + band system of BeH + , BeD + , and BeT + has been photographed at high resolution and rotationally analyzed. Together with literature data (W. W. Watson and R. F.Expand
Accurate Adiabatic Treatment of the Ground State of the Hydrogen Molecule
Accurate ground‐state energies of the hydrogen molecule have been computed using wavefunctions in the form of expansions in elliptic coordinates and including explicitly the interelectronic distance.Expand
...
1
2
3
4
5
...