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• W2007293764 abstract "Attention is drawn to the often-neglected alternative sets of force constants which may reproduce equally well data which in number and precision are otherwise adequate to define all the parameters of the general force field. An empirical survey of (2 × 2) vibrational problems illustrate some of the circumstances under which these arise. Where symmetrical isotopic substitution or physical intuition fails to provide evidence for discriminating between the alternative sets, asymmetric substitution succeeds in specified cases. Examples studied in detail include the E species of NF3, the B2 species of ketene and diazomethane and the Ag species of ethylene. In the latter case, two different force fields are current in which kc = c is either ~11 or ~9 mdynÅ. That the second of these is the correct one, is now shown by a study of 13C frequency shifts in H2CCD2. This result has important implications for the totally symmetric force constants of other molecules containing the methylene group, such as formaldehyde, allene, ketene, diazomethane, all of which exhibit the phenomenon of two equally plausible force fields." @default.
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• W2007293764 date "1971-09-01" @default.
• W2007293764 modified "2023-10-17" @default.
• W2007293764 title "On isotopic substitution and the choice between alternative sets of force constants; with special reference to the cases of ethylene, ketene, diazomethane and formaldehyde" @default.
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• W2007293764 doi "https://doi.org/10.1016/0584-8539(71)80241-6" @default.
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