Abstract
The product of the reduced inertia J r of a dipolar molecule and the square of the far infrared absorption maximum wave-number ν max that it displays in dilute solution is shown, using a three-parameter Mori/itinerant oscillator model, to be related to the mean-square action on the molecule and hence by a simple argument to the solute volume of rotation V. Estimates of V have been made for seventeen rigid molecules (mainly substituted phenyls) and their ν max values have been measured in decalin solution at 293 and 110 K. Provided allowance is made for translation—rotation coupling in four cases, the derived relation I r ν 2 max = (8a a 2 c 2 kT) −1 V 2 P(0) is found to be approximately obeyed at both temperatures with P(0) (the solute-independent mean-square torque acting on a molecule of unit V) having a value of 4.0 × 10 17 (N m −2) 2 at both temperatures. It should now be possible to predict μ max for other solutes in decalin if their structures are known.
Published Version
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