On the barrier to molecular axial rotation in crystalline benzene

✍ Scribed by S.T. Howard; J.A. Platts; K. Woźniak

• Publisher: Elsevier Science
• Year: 1995
• Tongue: English
• Weight: 349 KB
• Volume: 239
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(95)00487-o

✦ Synopsis

The barrier to axial rotation of a benzene molecule in crystalline benzene has been computed by ab initio methods. A cluster consisting of a central molecule surrounded by its four nearest neighbours was treated at the Hartree-Fock level. Beyond this, the lattice was represented by (potential-derived) point charges placed at the nuclear positions. The energy barrier obtained in the best model was I0.1 kJ mol -I, which compares with 16.8 kJ mol -l found by relaxation time solid-state NMR measurements. A point charge-only lattice model gives a somewhat smaller estimate of the barrier height.