Vibrational anharmonicity in octahedral<i>XY</i><sub>6</sub>molecules

Hodgkinson, D.P.; Heenan, Richard K.; Hoy, A.R.; Robiette, A. G.

doi:10.1080/00268978300100141

Cited by 28 publications

(14 citation statements)

References 25 publications

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“…13, albeit subject to the corrections pointed out by Gray and Robiette 11 as well as introducing a factor of 1/2 in front of the d 3344t term in T 34 , in agreement with Ref. 16.…”

Section: A Constructing and Validating A Quartic Potential Hypersurfacesupporting

confidence: 82%

Evidence of Fermi resonance in core-ionized methane

Karlsen

Børve

2000

The Journal of Chemical Physics

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A full quartic potential energy surface is determined for core-ionized methane and used to investigate coupling between vibrational modes. A strong Fermi resonance is found between the first excited state of the symmetric stretching mode ν1′ and a doubly excited bending mode, whereas the corresponding interaction is less pronounced for v1′=2. In terms of the carbon 1s photoelectron spectrum of methane, the net effect of the mode coupling is to reduce the apparent contribution from anharmonicity to peak positions. The contribution from anharmonicity to the intensity of each peak is dominated by cubic and quartic terms in the symmetric stretching coordinate, and remains significant. This resolves a paradox pointed out in a recent experimental work [Carroll et al., Phys. Rev. A 59, 3386 (1999)].

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“…13, albeit subject to the corrections pointed out by Gray and Robiette 11 as well as introducing a factor of 1/2 in front of the d 3344t term in T 34 , in agreement with Ref. 16.…”

Section: A Constructing and Validating A Quartic Potential Hypersurfacesupporting

confidence: 82%

Evidence of Fermi resonance in core-ionized methane

Karlsen

Børve

2000

The Journal of Chemical Physics

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“…The vibrational analyses were performed using a modified version of the SPECTRO program [58,59] running on an IBM RS6000 workstation at NASA Ames and the DEC Alpha at the Weizmann institute. The alignment conventions for the anharmonic constants of a spherical top follow the work of Hecht [60] and general formulae for these constants were taken from the paper by Hodgkinson et al [61]. Similar to previous work [3,62] on the spherical tops Be 4 and CH 4 , the accuracy of the various spectroscopic constants was verified by applying opposite mass perturbations of ±0.00001 a.m.u.…”

Section: Methodsmentioning

confidence: 71%

Accurate ab initio anharmonic force field and heat of formation for silane

Martin¹,

Baldridge²,

Lee³

1999

Molecular Physics

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From large basis set coupled cluster calculations and a minor empirical adjustment, an anharmonic force field for silane has been derived that is consistently of spectroscopic quality (±1 cm −1 on vibrational fundamentals) for all isotopomers of silane studied. Inner-shell polarization functions have an appreciable effect on computed properties and even on anharmonic corrections. From large basis set coupled cluster calculations and extrapolations to the infinite-basis set limit, we obtain TAE 0 =303.80±0.18 kcal/mol, which includes an anharmonic zero-point energy (19.59 kcal/mol), inner-shell corre-

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“…W vanishes for the ground vibrational state and is listed for low vibrational states of XY 4 in table III of [18]. Expressions for Xrs, Grs, Tr,~, S~s are given in [18] for XY 4 and in [16] for XY 6.…”

Section: Results : Vibrational Eerectsmentioning

confidence: 99%

“…To the order in which we work only 22 (XY4) and 41 (XY6) quartic coefficients contribute to the property expectation value. The symmetry relations between non-zero coefficients may be derived from table 2 of [15] (for XY4) and tables 3 and 4 of [16] (for XY6). For each anharmonic constant ~rst, ~rslu (n) listed in [15,16] there is a corresponding Pr~t, Pr~tu (n).…”

Section: Introductionmentioning

confidence: 99%