Abstract
The absolute absorption intensities of the fundamental vibration bands in ammonia and phosphine have been measured. Normal coordinates are calculated for each of the vibrations and the intensities interpreted in terms of bond moments μ and their derivatives ∂μ/∂r. Values of ∂μ/∂r for the NH and PH bonds in the A1 mode are 0.6 and 1.2 D/A, respectively; in the E mode the corresponding values are 0.2 and 0.8 D/A. Values of the vibrational bond moments found are 1.0 D (A1) and 0.5 D (E) for the NH bond; 0.7 or 0.5 D (A1) and 1.2 or 0.6 D (E) for the PH bond. The relation of these vibrational bond moments to the molecular dipole moment and the moment (μu.p.) of the unshared pair of electrons is discussed in detail. After corrections have been applied for changes in magnitude and direction of μu.p. during the vibrations, the results for NH3 are compatible with the following static moments: μNH∼0.7D(H+),μu.p.∼0.7D.The data for PH3 are less internally consistent. ``Likely'' moments, taken from the A1 bending vibration, are μPH∼0.2(H+), μu.p.∼0.2D.
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