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- W2059936143 abstract "The infrared A E52 g ← X G32 g electronic band system of ReF6 near 2μ has been recorded in the vapor and polycrystalline solid phase. Features of the vibrational analysis are: (i) the system has a magnetic-lipole-allowed origin hand, accompanied by electric-dipole-vibronic origins associated with single quanta of the enabling vibrations ν4(f1u) and ν6(f2u); (ii) short progressions occur in the totally-symmetric mode ν1(a1g), indicating a small Franck-Condon shift; (iii) upper state ν5′(f2g) progressions of 2–3 members are present in both the magnetic-dipole and electric-dipole vibronic components; and (iv) weak 1-0 transitions in ν2 (eg) are observed only in the electric lipole component. The ν5′ progressions are harmonic and provide def nite physical evidence of a trigonal Jahn-Teller effect, involving the mode ν5 in the ground (G32g) state. Analysis of relative intensities of the members of three such progressions, using a linear coupling model for the Jahn-Teller effect, is found to be consistent with a “mild” coupling strength, 0.2 < D5 < 0.4. ReF6 possesses a single ν5 Raman fundamental at 247 cm−1, although two are allowed by the Jahn-Teller effect. This interval reappears in the electronic spectrum in a way favoring one of these two assignments, and this permits an independent estimate of D5 = 0.42. The inferred potential energy stabilization due to trigonal distortion is 74 cm−1, while the lowest vibronic level occurs well above this at 114 cm−1. Vibration frequencies deduced for the A E53g state from the 15°K spectrum are: ν1(ag) = 711, ν2(eg) = 661, ν4(f1u) = 266, ν5(fzg) ≡ 297, and ν6(f2u) = 178 cm−1." @default.
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- W2059936143 date "1971-06-01" @default.
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- W2059936143 title "The near-infrared band system of rhenium hexafluoride" @default.
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- W2059936143 doi "https://doi.org/10.1016/0022-2852(71)90071-3" @default.
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