High-resolution spectra of the infrared-active stretching fundamental ν3 of 238UF6 have been obtained between 620.6 and 633.5 cm−1 using tunable semiconductor diode lasers. Interference from hot bands was suppressed by cooling the UF6 in a supersonic expansion, and useful monomer concentrations were produced with effective temperatures of <100 K. Portions of the band from P(77) to R(66) are illustrated. All transitions from the vibrational ground state have been assigned, and the Q branch has been fully analyzed. A total of 43 line frequencies and 110 frequency differences extending in J to P(77), Q(91), and R(67) has been used to fit seven spectroscopic constants. The ground- and excited-state values of the rotational constant B could be individually determined, and the U–F bond length in the ground vibrational state is r0=1.9962±0.0007 Å. The Q branch of 235UF6 has also been analyzed and the 235UF6–238UF6 ν3 isotope shift measured to be 0.603 79±0.000 17 cm−1. The isotope shift and the Coriolis constant ζ3 have been used to refine the general quadratic intramolecular force field of UF6, and the Cartesian displacement coordinates of both infrared-active fundamentals are illustrated and compared with those of SF6.
An improved microwave cavity technique for measuring dielectric constants was used to determine the molar polarization, dipole moment, and nonideality of UF6, freon-114, C4Cl3F7, and C6H6. Nonideality parameters were calculated for ClF3 from previous data.
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