Infrared, Raman, and ultraviolet spectra of M+ClF- species in solid argon

Prochaska, Eleanor S.; Ault, Bruce S.; Andrews, Lester

doi:10.1021/ic50174a039

Cited by 8 publications

(2 citation statements)

References 12 publications

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“…These bands have been assigned to the C1-F stretching mode in the appropriate complex, and these represent the largest shifts seen to date. The parent molecular anion C1F-, for comparison, has its stretching mode near 350 cm -1, depending on the metal cation employed [90]. The shifts here are on the same order of magnitude, suggesting a roughly 50% reduction in stretching force constant, and substantial charge rearrangement in the complex.…”

Section: Intermediate Complexes Of Highly Reactive Reagentsmentioning

confidence: 74%

Matrix isolation studies of reactive intermediate complexes

Ault

1988

Reviews of Chemical Intermediates

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Section: Intermediate Complexes Of Highly Reactive Reagentsmentioning

confidence: 74%

Matrix isolation studies of reactive intermediate complexes

Ault

1988

Reviews of Chemical Intermediates

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“…The former of these is found to have [7] a symmetric bent structure and the latter to have [8] a slightly asymmetric linear structure in the ground state. Ab initio SCF calculations of Ungemach and Schaefer [2] support the experimental structure of ClF2, but no such theoretical study has yet been made to substantiate the observed structure of c13.…”

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confidence: 99%

Electronic structure of triatomic interhalogens

Sannigrahi

1982

Int J of Quantum Chemistry

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Although a number of trihalide ions have long been experimentally characterized [I], very little is known about the parent neutral radicals. Available experimental [ 11 and ab initio theoretical [2,3] Ungemach and Schaefer [2] support the experimental structure of ClF2, but no such theoretical study has yet been made to substantiate the observed structure of c13. The CND0/2 (spd) calculations of Vasini and Castro [9] on C I S and CI3 indicate that both the radicals possess a linear symmetric structure. In view of the fact that they obtained very irregular angular potential (AP) curves (the AP curve of C I S shows a minimum at 100' and constant energy in the range of 17Oo-18O0, whereas the AP curve of C13 shows minima at looo, 160°, and 180') and performed the SCF iterations on C13 with a precision of hartree, their conclusion is very much questionable. Deb et al.[ID] also performed CND0/2 (spd) calculations on CIF2 and predicted a linear symmetric structure. It is, however, well known [l 11 that CND0/2 (spd) calculations with original parameters [12] overestimate the bond angles and underestimate the bond lengths. We therefore carried out CND0/2 and INDO calculations [13] on CIF2 and c 1 3 using sp basis set, and observed that both of them possess symmetric bent structure. In order to obtain more information about the structural pattern of triatomic interhalogens in general, we have performed similar calculations on four additional systems, namely, F3, FFCl (the asymmetric conformer of CIFz), ClFCl (the symmetric conformer of CIzF), and ClClF (the asymmetric conformer of C12F). Since it is not convenient to discuss molecular electronic structure on the basis of composition and population of the occupied MO' s obtained from UHF-type calculations, we have also performed RHF-type calculations on some of the molecule.For the UHF calculations we have followed the same method of calculations as outlined in our previous paper [I 31. The RHF The calculated ground state geometry of F3, FCIF, FFCI, CIFCI, CICIF, and CI3 is given in Table I along with the available experimental and ab initio theoretical values. We carried out RHF calculations only for FCIF, ClFC1, and C13 since we thought that the results of these calculations might be considered as representative of the entire series. Considering the equilibrium geometrical parameters in Table I we find that with the exception of CIFCI, all the molecules are predicted to have a bent structure. The RHF calculations yield somewhat smaller interbond angles for the bent molecules than the corresponding UHF calculations. A similar trend isbbserved when the results of CND0/2 and INDO calculations are compared. As regards

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