Observation of three intermolecular vibrational states of ArHF

Dvorak, M. A.; Reeve, Scott W.; Burns, William A.; Grushow, Alexander; Leopold, K. R.

doi:10.1016/s0009-2614(91)85082-8

Cited by 32 publications

(6 citation statements)

References 23 publications

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“…We have employed this the lth rotational state, I jm), and El is the energy associated method in our calculations and find that using the spherical with the j rotational level of the lth state. The time-dependent average of the potential shows no significant difference bequantum equations of motion are then given by tween the deflection or opacity functions from an Ehrenfest average calculation, but with a substantial savings in compu- [7] ih t k = C cl ~k l ( t ) exp (iaLlt) tational time.…”

Section: Iib Time-dependent Methodsmentioning

confidence: 99%

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Semiclassical study of sudden approximations for rotationally inelastic scattering of Ar + HF

Barrett¹,

Mayne²,

Keil³

et al. 1994

Can. J. Chem.

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, 985 (1994)."Exact" quantum close coupled (CC) and infinite-order sudden approximation (IOSA) calculations have been carried out for the Ar + HF system on an accurate potential energy surface. The differential cross sections from the IOSA calculations show marked differences from the CC results. We find that the energy sudden component of the IOSA breaks down in a different manner for small and large impact parameters, significantly shifting and distorting the state-to-state differential cross sections. We also find that the centrifugal sudden approximation alone reproduces all features of the full semiclassical calculations quite faithfully. Through the use of several rotational sudden approximations, including a semiclassical version of the IOSA, we identify how the differences between the CC and IOSA results arise.

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Section: Iib Time-dependent Methodsmentioning

confidence: 99%

“…Spectroscopic data for the Ar+HF system have been used by Hutson (3) to obtain a potential of excellent quality (7) in the attractive region, hereafter referred to as the "Hutson H6" potential. Scattering data, in the form of final state selected DCS from crossed molecular beam experiments on Ar+HF, have also recently been obtained (8).…”

Section: Introductionmentioning

confidence: 99%

Semiclassical study of sudden approximations for rotationally inelastic scattering of Ar + HF

Barrett¹,

Mayne²,

Keil³

et al. 1994

Can. J. Chem.

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“…Finally, it is useful to point out here that, in general, the lowest-energy configurations of these and larger Ar n OH clusters ͑nу6, see below͒ can be related to the global minima of pure Ar nϩ1 clusters ͑tetrahedron for Ar 4 , trigonal bipyramid for Ar 5 , octahedron for Ar 6 , etc.͒, 18,47,48 with OH playing the role of an Ar atom and its H-atom end pointing towards Ar n . The only exception is Ar 4 OH, where the C 3v structure ͓Fig.…”

Section: Ar N Oh Nä3-5mentioning

confidence: 96%

“…The understanding that can be gained is exemplified by complexes and clusters formed between HF and Ar. In the period 1981-1991, extensive high-resolution spectra of the Ar-HF and Ar-DF Van der Waals complexes were observed in the microwave, [1][2][3] far-infrared, 4 and mid-infrared [5][6][7][8] regions of the spectrum. Then, in 1992, Hutson 9 used the spectra in a combined least-squares fit to obtain an accurate and reliable model of the Ar-HF pair potential.…”

Section: Introductionmentioning

confidence: 99%

Clusters containing open-shell molecules. II. Equilibrium structures of ArnOH Van der Waals clusters (X2Π, n=1 to 15)

Bačić

Hutson

2002

The Journal of Chemical Physics

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The equilibrium and low-lying isomeric structures of ArnOH (X2Π) clusters for n=1 to 15 are investigated by simulated annealing calculations. Potential energy surfaces are obtained by a pairwise-additive approach, taking into account the open-shell nature of OH X2Π and including spin-orbit coupling. It is found that the spin-orbit coupling suppresses the Jahn–Teller effect, and many of the clusters have high-symmetry structures (Cnν with n>2) which would be forbidden in the absence of spin-orbit coupling. The structures are generally similar to those previously found for the closed-shell systems ArnHF and ArnHCl, but different from those for the open-shell systems ArnNO and ArnCH. This is because Ar–OH (X2Π), like Ar–HF and Ar–HCl but unlike Ar–NO and Ar–CH, has a near-linear equilibrium structure. ArnOH clusters for n up to 6 have all Ar atoms in a single shell around OH. In the clusters with n=7 to 9, OH is under a pentagonal pyramid formed by six Ar atoms, while the others bind to its exterior, away from OH. For n=10 to 12, the minimum-energy structures have OH inside an Arn cage, which is essentially icosahedral for n=12 but has vacancies for n=10 and 11. For n>12, the extra Ar atoms begin to form a second solvation shell. The global minimum of ArnOH may be constructed from the minimum-energy structure of Arn+1 by replacing one Ar atom with OH.

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“…Presently, a total of 30 vibrational states have been spectroscopically characterized in various wavelength regions, ranging from radiofrequency, 1 microwave, 2 far-infrared, 3 mid-infrared, 4-9 through near-infrared. 10,11 The spectroscopic investigations are a sensitive probe of the Ar-HF interaction potential, not only near the potential minimum but also for angular and increasingly large radial excursions.…”

Section: Introductionmentioning

confidence: 99%

Weak bond stretching for three orientations of Ar–HF at vHF=3

Chuang

Higgins

et al. 2000

The Journal of Chemical Physics

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Prediction of metastable metal-rare gas fluorides: FMRgF ( M = Be and Mg; Rg = Ar , Kr and Xe) Stabilization and rovibronic spectra of the T -shaped and linear ground-state conformers of a weakly bound raregas-homonuclear dihalogen complex: He Br 2The C 3 -bending levels of the C 3 -Ar complex studied by optical spectroscopy and ab initio calculation Three new ArHF (v HF ϭ3) states, ͑3001͒, ͑3101͒, and ͑3111͒, have been observed between 11 350 and 11 420 cm Ϫ1 by the hot band transitions from ͑0001͒ using intracavity laser induced fluorescence. The term values and rotational constants of these levels are: ͑3001͒ 0 ϭ11 385.928 98(28) cm Ϫ1 , Bϭ0.095 546(32) cm Ϫ1 ; ͑3101͒ 0 ϭ11 444.258 12(68) cm Ϫ1 , B ϭ0.090 617(37) cm Ϫ1 ; and ͑3111͒ 0 ϭ11 456.076 51(36) cm Ϫ1 , Bϭ0.091 863(14) cm Ϫ1 . Observation of the ArHF ͑3001͒ state provides the van der Waals stretching frequency for ArHF at vϭ3, namely 46.8945(4) cm Ϫ1 ϭ(3001) -(3000). This value shows an increase of 8.208 cm Ϫ1 ͑21%͒ upon HF vϭ3←0 valence excitation. The stretching frequency for the T shaped ArHF is (3111) -(3110)ϭ33.7055(5) cm Ϫ1 . This value is only 7% greater than that observed at vϭ1. The (v HF 101) ⌺ bend-stretch combination state, corresponding to ( s ϭ1) of the Ar-FH configuration, has not been observed at v HF ϭ0 -2. The stretching frequency here is (3101) -(3100) ϭ31.8178(8) cm Ϫ1 . The soft-mode frequencies reveal strong bend-stretch coupling in the complex. Excellent agreement ͑within 0.3 cm Ϫ1 ͒ is found between experiment and prediction from Hutson's H6͑4, 3, 2͒ potential ͓J. Chem. Phys. 99, 9337 ͑1993͔͒, for the three new levels. Large basis set coupled cluster calculations ͓CCSD͑T͔͒ of the Ar-HF intermolecular potential surface, V(R,,r), are presented for rϭ0.6-2.0 Å and ϭ0 -180°on a grid with 15°spacing. This is an enlargement of the HF valence coordinate of more than double the equilibrium value. The dependence of the intermolecular potential upon the HF valence coordinate, r, is very anisotropic, being maximal for ϭ0°and becoming essentially independent of r for у45°.

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Observation of three intermolecular vibrational states of ArHF

Cited by 32 publications

References 23 publications

Semiclassical study of sudden approximations for rotationally inelastic scattering of Ar + HF

Semiclassical study of sudden approximations for rotationally inelastic scattering of Ar + HF

Clusters containing open-shell molecules. II. Equilibrium structures of ArnOH Van der Waals clusters (X2Π, n=1 to 15)

Weak bond stretching for three orientations of Ar–HF at vHF=3

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