## Abstract

The nuclear magnetic resonance absorption spectrum and the spin-lattice relaxation time have been measured for the protons in three isotopic species of benzene in polycrystalline form between 75 and 278 degrees K. The three species were C$_{6}$H$_{6}$, C$_{6}$H$_{5}$D and 1.3.5-C$_{6}$H$_{3}$D$_{3}$. For all three species the measured spectrum has its full rigid lattice width below 90 degrees K. A method of analysis is developed which makes it possible to derive separately the intramolecular and the intermolecular contributions to the second moment (mean square width) of the spectrum from the measured second moments, without the necessity of knowing the crystal structure. From the intramolecular contribution it is found that the separation of neighbouring protons in the C$_{6}$H$_{6}$ molecule is 2$\cdot $495 $\pm $ 0$\cdot $018 angstrom. The intermolecular contribution is in agreement with a value calculated from a knowledge of the crystal structure. On warming from 90 to 120 degrees K the spectrum for all three species narrows considerably. From 120 degrees K to the melting-point (278$\cdot $7 degrees K) the second moments remain almost constant. The second moment separation procedure is also applied in this range and leads to the conclusion that the narrowing is caused by reorientation of the molecules about their hexad axes in the crystal lattice. Analysis of the measurements of the spin-lattice relaxation time shows that for all three species the reorientation process is governed by an activation energy of 3$\cdot $7 $\pm $ 0$\cdot $2 kcal/mole. The reorientation frequency is of the order of 10$^{4}$ c/s at 85 degrees K and rises to a value of the order of 10$^{11}$ c/s just below the melting-point. The relationship between the present experimental results and recent measurements of the Raman spectrum of solid benzene is discussed. Finally, consideration is given to the application to other materials of methods of separating the intra- and intermolecular contributions to the second moment.