Determining repulsive potentials of InAr from oscillatory bound→continuum emission

Fawzy, Wafaa M.; Roy, Robert J. Le; Simard, Benoît; Niki, Hideaki; Hackett, P. A.

doi:10.1063/1.464663

Cited by 26 publications

(11 citation statements)

References 14 publications

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“…Similarly, Fawzy et al (28) were able to carry out a semiclassical inversion of their data to yield a pointwise representation of not able to obtain such complete information on the two states (X, 211312, A ,Cf) correlating with the spin-orbit excited asymptote In(5p 2~3 / 2 ) + Ar.…”

Section: Discussionmentioning

confidence: 99%

“…Fawzy et al (28) also employed the intensities of the maxiina in their InAr bound-free spectra to estimate the B 2~f -XI 211 ,,, transition moment function. They found that this function is approximately a constant over the range 2.9 to 3.8 A.…”

Section: Discussionmentioning

confidence: 99%

“…The wavenumbers of the extrema in the spectra determine the potential energy curves, while intensity information can be used to derive the transition moment function. Fawzy et al (28) have recently reported such a study for the determination of the repulsive potential in the InAr van der Waals molecule. Fortuitously, this system also involves a group 13 metal -rare gas complex and is a higher homologue of BAr.…”

Section: Introductionmentioning

confidence: 99%

“…The InAr X 211 spin-orbit splitting is much greater than that in BAr so that the B 2~+ -XI 211112, X2 2r13/2 emissions are resolved. It was possible to invert the experimental data to obtain a pointwise repulsive potential for the InAr(X1 211112) state (28). Overlapping of the B 2C+ -X 211312 and B 2X+ -A 2C+ emission prevented extraction of the repulsive potentials of the lower states of these transitions by this inversion method.…”

Section: Introductionmentioning

confidence: 99%

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Bound–free B²Σ⁺ –X²Π, A²Σ⁺ emission in the BAr van der Waals complex

Hwang¹,

Dagdigian²,

Alexander³

1994

Can. J. Chem.

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This pnper is dedicated to Professor John C. Polclnyi on the occasion ofhis 65th birthday E m s o o~ HWANG, PAUL J. DAGDIGIAN, and MILLARD H. ALEXANDER. Can. J. Chem. 72, 821 (1994).Spectrally resolved bound-free fluorescence emission spectra for the excitation of several vibrational levels in the excited B 2x+ electronic state of the van der Waals molecule " B A~ are presented. This excited state emits to the ground X 2n and low-lying A 'z+ states, both of which correlate with the ground state atomic asymptote B(2p 2~) + Ar. Because of the large differences in equilibrium internuclear separations, the emission occurs mainly to the repulsive walls. In order to gain more information on this portion of the potential energy curves, the experimental emission spectra were compared with simulated spectra derived from ob initio calculated B-Ar interaction potentials. The simulated spectra reproduce the experimental spectra well if the lower-state potential energy curves are shifted slightly inward. This discrepancy is consistent with our previous observation that the a b irlitio calculations slightly overestimate the vibrationally averaged internuclear separation, which we determined experimentally. This reflects the difficulty of accurately calculating weak van der Waals interaction energies. Introduction Supersonic beam and laser spectroscopic methods have been extensively employed to observe transitions between bound vibrational levels of weakly bound diatomic metal -rare gas van der Waals complexes, as illustrated by recent representative studies involving metals in a number of chemical groups (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17). With the resulting derived spectroscopic data, considerable information has been obtained on the attractive portions of the potential energy curves of the ground and excited electronic states. It would also be interesting to extract similar information on the repulsive parts of these curves from analysis of continuum spectra.In a recent paper (17), we reported a collaborative experimental and theoretical study of the BAr van der Waals complex. This metal -rare gas complex contains the lightest element of the group 13 family and has a relatively small number of electrons so that accurate electronic structure calculations could be carried out for the ground and excited electronic states of this system. Similar all-electron calculations on other weakly bound metal -rare gas complexes have performed (1 8-2 1). A number of the complexes of heavier members of this series (AlRg, InRg) have been spectroscopically studied by other groups (1 1-16). In our study of BAr, we observed (17), using laser fluorescence excitation of a pulsed supersonic beam, a progression of

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Bound–free B²Σ⁺ –X²Π, A²Σ⁺ emission in the BAr van der Waals complex

Hwang¹,

Dagdigian²,

Alexander³

1994

Can. J. Chem.

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“…On the basis of bound-free fluorescence spectra, the ground states of the CdNe, CdAr, CdKr (17), and MgXe (18) molecules have been described in terms of a Buckingham potential. The structured fluorescence continua of NaAr provided information on the repulsive part of the ground state potential which was found to be a modified Morse curve (19) and, in another investigation, the repulsive part of the InAr ground state PE curve was determined from an oscillatory bound-free emission spectrum (20) with the help of an inversion procedure proposed by Child et al (21). Hishikawa et al (22) deduced the long-range interaction potential for the HgAr A state from a deperturbation analysis of a rotationally resolved excitation spectrum of the B state.…”

Section: Introductionmentioning

confidence: 99%