High-resolution FTIR and millimeter-wave study of FClO3: Ground state rotational constants including A0, structure, and the ν2, ν3, ν5, and ν6 excited states

Rovibrational Analysis of the ν6 Bands of Four Symmetric Isotopomers of FClO3

“…As already noted in Ref. (2), the K ⅐ ⌬K Ͼ 0 subbands are located below the K ⅐ ⌬K Ͻ 0 ones, contrary to the usual situation in prolate symmetric tops with a large A/B ratio. Since the nuclear spin of both 16 O and 18 O is zero, only the K ⅐ ⌬K ϭ 3p subbands are observed, so that successive Q branches are separated roughly by the quantity 6 ( AЈ Ϫ BЈ Ϫ A) ϭ Ϫ283/Ϫ284/Ϫ297/Ϫ298 ϫ 10 Ϫ3 cm Ϫ1 for the different isotopomers.…”

“…As a consequence, strong and isotope-selective effects of the ⌬K ϭ Ϯ3 interaction have been observed in the vibrational ground state and in the v 5 ϭ 1 state of these species (5). It is likely that similar causes are responsible for the very small intensity of the 3 fundamental bands of (35, 16) 2 and (37, 16) and the almost vanishing intensity of 3 in (35, 18) and (37, 18), whereas the ␣ 3 B constants have a different sign and size in the 16 O and 18 O species (6). The present work deals with the v 6 ϭ 1 states of the same isotopomers.…”

“…Perchloryl fluoride, FClO 3 , a symmetric top molecule belonging to point-group C 3v , has been the subject of a systematic study (1)(2)(3)(4)(5)(6) which brought out several specific characteristics mostly due to the fact that this molecule is nearly spherical. This quasi-spherical character can be expressed by the ratio ␥ ϭ ( A 0 Ϫ B 0 )/A 0 , the value of which is 0.0624 for F 35 3 , ␥ ϭ 0.0154 and 0.0157, respectively.…”

The Mystery of a Band Vanishing upon Isotopic Substitution: The Case of the v3 = 1 State of FClO3

“…What could be expected instead is that as a molecule approached T d symmetry, two pairs of A 1 , E bands would merge to make two also infrared-active F 2 fundamentals of a tetrahedral molecule. It is true that 5 suggesting that the molecule in question departs significantly from a tetrahedral structure. This conclusion is supported independently by results of Pawelke's calculations (8), which resulted in the following charges on individual atoms:…”

Microwave Fourier Transform Spectroscopy of Perchloryl Fluoride:19F35/37Cl16O3and19F35/37Cl16O218O

“…Burczyk et al (12)(13)(14) reported extensive analyses of Perchloryl fluoride, FClO 3 , was first obtained by Bode and high-resolution IR and millimeter-wave spectra. In general, Klesper in 1951, but was believed to be chloryl hypofluorite, a sample monoisotopic in 35 Cl was investigated, though in O 2 ClOF (1).…”