Vibration Rotation Interaction in OH and the Transition Moment

J. Anketell, R. C. M. Learner
1967 Proceedings of the Royal Society A  
A re-ex am in atio n of th e in te n sity d istrib u tio n in th e A 2U -X 27T u ltra v io le t b a n d s of O H le a d s to a v ib ratio n al tra n sitio n m o m en t R ev(r) = ex p { -(5-97 + 0T2)r}, w here r is th e in tern u clear d istance in A ngstrom s. I t is show n t h a t th is value for th e tra n sitio n m o m en t will n o t explain th e v ariatio n of in te n sity w ith ro ta tio n a l q u a n tu m n u m b er. T he in te ra c tio n of ro ta tio n a n d electronic m otion leads to
more » ... c m otion leads to a second, ro ta tio n a l, tra n sitio n m o m en t. T his te rm is rela te d to th e centrifugal d is to rtio n of th e m olecule, a n d for th e (0, 0 ) b a n d is given b y R eJ{r) = exp { + (3-60± 1-0) x 10-4J ( J + 1}. W ith in th e (0, 0) b an d th e co m b in atio n of these tw o m o m en ts is e q u iv alen t to a single fu n ctio n R e(r) = exp { -(2-67 + 0-9)r}. I n consequence (0, 0) b a n d v ib ra tio n -ro ta tio n in te ra c tio n an d te m p e ra tu re corrections rem ain as given b y L earn er (1962). T he relativ e J d ep en d en t v ib ra tio n a l tra n sitio n probab ilities for th e re st of th e system are corrected. T he effect of th e ro ta tio n a l tra n sitio n m o m en t on th e m easu rem en t of ro ta tio n a l te m p e ra tu re is discussed for b o th O H an d o th er d iatom s.
doi:10.1098/rspa.1967.0213 fatcat:mgkvowwxq5dlfixvvntbqxa23u