Clarification of the assignment of the electronic spectrum of hydrogen chloride based on ab initio cl calculations

Bettendorff, Marc; Peyerimhoff, Sigrid D.; Buenker, Robert J.

doi:10.1016/0301-0104(82)88026-9

Cited by 112 publications

(58 citation statements)

References 14 publications

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“…The small singlet-triplet splitting is not particularly surprising since we are dealing with Rydberglike states (cf. [27]). Similarly, the l'3A states differ little from the 21.3/i states since they both represent (r~Cs(5d) excitations, only with different Rydberg d orbital orientations.…”

Section: The ~'3ii and I'3a Statesmentioning

confidence: 93%

Ab initio MRD CI calculations on the cesium hydride (CsH) molecule

Carnell

Peyerimhoff

Heß

1989

Z Phys D - Atoms, Molecules and Clusters

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Ab initio multi-reference configuration interaction (MRD CI) calculations were carried out for the potential energy curves of the first 17 electronic states of the CsH molecule up to large bond distances (20 bohr). The aS+ states were also calculated by means of relativistic all-electron SCF and CI using the spin-free no-pair operator with external field projectors. For the low-lying states, the spectroscopic parameters were determined. Dipole moments as well as the transition dipole moments: # ( X ' S +~ A ~ Z+), #(X 1 Z + B ~ Z+), # ( A ~ S + ~ B ~ S+), were also calculated. Non-relativistic and relativistic results are compared. An analysis of the interactions in the 1,3S+ states is also proposed.

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Section: The ~'3ii and I'3a Statesmentioning

confidence: 93%

Ab initio MRD CI calculations on the cesium hydride (CsH) molecule

Carnell

Peyerimhoff

Heß

1989

Z Phys D - Atoms, Molecules and Clusters

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“…The factor of 2 difference between z and zЈ is of no consequence on the flexibility or convergence properties of the model, but simply leads to different definitions for most of the fitted parameters, as well as the definition of z (ϱ) in Eq. [45] below. We prefer to retain the traditional definition of the z variable.…”

Section: Least-squares Fittingmentioning

confidence: 95%

The Radial Hamiltonians for the X1Σ+ and B1Σ+ States of HCl

Coxon

Hajigeorgiou

2000

Journal of Molecular Spectroscopy

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“…This figure also makes clear that the lower 3//Rydberg states are also affected to some extent by the presence of the repulsive valence state of the same symmetry, since the unperturbed 3//gl (rc~3s) state potential curve would be expected to run roughly parallel to that for the 3A R 0z~3pz0 state but instead shows considerable deviation therefrom; tbr small bond lengths note also that the 3HR2 (7c-~3pa), 3A R (n--+3p~z) and 3Z~i (rc~3pzc) are almost isoenergetic for larger HF separations, as one would expect according to the simple model, but are split further apart at small bond lengths due to the different perturbations with the respective valence-shell states. Finally it is interesting that the pattern in HC1 is similar in principle but that the effect on the measured lines is much less marked in practice since the B state potential curve crosses the Rydberg manifold at higher vibrational-levels [27], i.e. not at roughly the bottom of the Rydberg potential curve (which yields the maximum scrambling) but farther away towards larger internuclear separations.…”

Section: Z+-x1z+mentioning

confidence: 94%

Ab initio Cl calculation of the effects of Rydberg-valence mixing in the electronic spectrum of the HF molecule

et al. 1982

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Experimental studies of the HF molecular spectrum have heretofore been unable to arrive at a suitably consistent theoretical assignment for the various measured band systems therein. To aid in this pursuit a series of ab initio C1 calculations in an AO basis containing 40 contracted gaussians has been carried out to an accuracy which is close to the full C1 limit as a result of the use of energy extrapolation techniques described elsewhere. In addition to obtaining generally quite good agreement with experimental spectroscopic constants including the dissociation energy, this treatment allows for a careful description of the change in composition of the HF ground state from ionic to covalent character as molecular stretching occurs, as well as a good representation of the upper B 1Z+ state with which it undergoes a strongly avoided crossing. The repulsive branch of the latter potential energy curve is shown to intersect the Rydberg 1Z+ manifold at relatively short bond distances, leading to a series of mixed valence-Rydberg states which are ultimately responsible for the large deviations from normal Rydberg series which are observed experimentally. Similar crossings of a---,~* and a~a* valence states with Rydberg species of 3'1/7 and/or 3Z+ symmetry are calculated to result in heavy mixing over only a relatively short range of bond distances, and thus do not produce the same magnitude of perturbations as do the 1Z+ states. Finally the calculated potential curve for the parent X2II ionic state for such Rydberg species also proves to be quite consistent with known structural data, giving independent evidence for the overall high level of accuracy of the theoretical treatment employed in the present work.

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Clarification of the assignment of the electronic spectrum of hydrogen chloride based on ab initio cl calculations

Cited by 112 publications

References 14 publications

Ab initio MRD CI calculations on the cesium hydride (CsH) molecule

Ab initio MRD CI calculations on the cesium hydride (CsH) molecule

The Radial Hamiltonians for the X1Σ+ and B1Σ+ States of HCl

Ab initio Cl calculation of the effects of Rydberg-valence mixing in the electronic spectrum of the HF molecule

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