Vibration–internal rotation–overall rotation interactions in CH3OH. II. Vibration introduced τ-dependence to the reduced kinetic energy coefficient for internal rotation

✍ Scribed by C.Richard Quade

• Book ID: 104151780
• Publisher: Elsevier Science
• Year: 2003
• Tongue: English
• Weight: 117 KB
• Volume: 219
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1016/s0022-2852(03)00028-6

✦ Synopsis

Vibration-internal rotation-rotation interaction theory has been used to calculate the s-dependence of F, the reduced kinetic energy coefficient for internal rotation for CH 3 OH from molecular structure. The leading term is À3:2 Â 10 À5 cos 3s as a fraction of F 0 . Smaller terms are 1:5 Â 10 À7 cos 6s and then À0:82 Â 10 À7 cos 2s and 5:0 Â 10 À10 cos 4s for the symmetry breaking terms of the vibrationally distorted molecule. These terms have not been included previously in torsion-rotation anaylses for CH 3 OH but should be compared with the fractional uncertainty in F 0 of AE7 Â 10 À7 . A rough estimate of the s-independent vibrational contributions to F 0 is of the order 4% with the largest contributors being the COH bend and OH stretch.