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Ira N. Levine - Molecular Spectroscopy-John Wiley & Sons (1975)

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655 views11 pages

Ira N. Levine - Molecular Spectroscopy-John Wiley & Sons (1975)

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jorge nogales
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curren 4 VIBRATION AND ROTATION OF DIATOMIC MOLECULES. 41 NUCLEAR MOTION IN DIATOMIC MOLECULES In Section 1.19, we showed how the Bora-Oppesheimer approximation separates the elecroni motions and noelse motions in a molecule. We Comsdered the elesttonie Schrodinger equations Setions 120 and 1.21 Se now study the nuclear Schrodinger egetion. Io this chapter, We Consider diatomic molecules Unlese otherwie sated, we wil restct, furseles to distomic molecules in 'S electron sats: the presence of tectonic spin or oral angular momentum complicates things. and wll be cncused in Section 411, Most dhtomie moerales have "2 electronic [round sates, notable exceptions being O, and NO. As wsua, we wil be ‘onsidering paphise molecules, neslecting itermolecuat interaction. “Te Schringer equation forthe noelear motion ofa diatomic molecule is, according to (1280) and (1.28, Pg Sm 93+ 008) be ‘tan 1) “The it to terms in brackets ate the kinetic-energy operators formule a And b the variable Ris he intemocear distance: the function UCR) isthe poteatial-nergy futon inching nacleae repulsion) for mele motion nd i ound by solving the letonse Seheodnger equation: dy yy 1 HE ‘rave fonction for mclese motion; Ey is the Ltal energy ofthe molecle Inching tanalaionalenetay ‘Equation (1 va wopartice problem. lo Section [.12 we showed that we can separste a worparle problem into two one-particle problems, provided that the potential energy & a function of only the relative coordinates of the two patiles” Since R involves only the ‘elative ‘coordinates ofthe nucle this conditions met. We conclode that Yom Yaa «a Fat Ea Ea «) ere Yan te wave fection or alton! motion of the mle as 2 whole 28d Gy the ave function forthe ineral moton of the tule relative oth oer The tsmstonal maton of the molecule Simply ads the constant quantity Ear tothe molecular energy, Wa Yn fOr Ppa aNd E for Ey, we have (Section 1.12) ™ " — ws E isthe total energy of the molecale (mile and electrons), excluding leanslatinal energy. The independent variables in (48) aze the elave pherial polar coordinates of the nucle (R,8y.¢y): the angle ad oy ve the orientation of the intermucear axis relative t0 the coordinate system showa in Fig. 41. Ths system ha te origina the moleclar center ‘of mass, and therefore translates tough space mith the molecules how ‘ve. des not rotate with the molecule, Since the soleclrfransationl motion iso no interest we ell the nonotting YZ aes the iaceficed Pet Spce an cline yen rt nce msn Since the potential eneray in (44) depends only on , we have 2 entra foce problem, andthe ests of Seton 1.1 show that Ge= FD Ou) (4s) where Ysa spherial harmonic, and Fs some function of R, We wse J {nd 6 istead of and forte angular-momentam quastam numbers. Conform with the standard notation for molecules. We have (Section 1.6) F012: «4 Mend aT IAS «sy “The rotational angular momentom of the race is YIC-+1) fi the com ponent ofthis angular momentam along the spacc-ned Z axis is Mh [Recall the two-particle rgd rotor, weated in Section 1.13, The diference tween (24) and the rgd rotor is that we are allowing the interaclear

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