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0342449369
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note
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Three factors appear to improve the signal-to-noise for rapid-scan methods relative to step-scan methods: (i) it is not necessary to wait for a lock-in to settle after each mirror step, (ii) multiplexing of signal frequencies is used, and (iii) interferogram oversampling requires no additional time. This is discussed more fully in Andrews, S. S.; Boxer, S. G. In preparation.
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0343318836
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note
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Early experiments were performed in a miniature Joule-Thompson refrigerator (MMR Technologies) operating at 80 K, but we found significant sample orientation in an electric field, leading to the development of the immersion cryostat. Poling may not be a problem for AC electric fields.
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0342449368
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note
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Data fitting was done with Macintosh software created for this purpose. The software and C language source code are available upon request.
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32
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0342449367
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note
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The parameters of a modified Voigt are: peak height, frequency, full width at half-maximum, and the Gaussian:Lorentzian ratio. These parameters are adjusted only to obtain a best fit to the absorption spectrum, and are not considered to have any physical meaning.
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0342449366
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note
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χ would be corrected to be 13% too small under the one-dimensional assumptions, contributing to a 7% error in the calculation of |Δμ|.
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35
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0011096338
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36
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25344474688
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Linear coupling between two modes results in redefined normal modes and a separation of the absorption peaks, whereas nonlinear coupling gives absorption between the peaks, and is responsible for Fermi resonance. The excess absorption is analogous to the coalescence seen in NMR spectra of dynamic systems (see e.g. Gasparro, F. P.; Kolodny, N. H. J. Chem. Educ. 1977, 54, 258-261).
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Atomic and molecular polarizabilities
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0004230584
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Worth Publishers: New York
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The transition state enthalpy is expected to be about 16 kJ/mol, from butane data (see e.g., Kemp, D. S.; Vellaccio, F. Organic Chemistry; Worth Publishers: New York, 1980; p. 472), implying an interconversion rate below 1 ms down to the 100 K glass transition temperature, which is fast compared to the freezing rate. Thus, low-temperature population ratios were computed for 100 K, with the assumption that the sample is at equilibrium before freezing and immobilized thereafter. Boltzmann population calculations use an enthalpy difference between anti and gauche conformations of 2.8 kJ/mol, a value found by AM1 calculations for the relevent nitriles.
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Organic Chemistry
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Vellaccio, F.2
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Cyanogen was synthesized by an adaptation of a method from: Janz, George J. Inorg. Synth. 1957, 5, 43-48.
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McQuarrie, D.A.1
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