ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
By using the vibration-rotation canonical functions, we show that the wave function for a vibration-rotation level (v, J) can be represented by ψvJ(r) = ψv (r)+Σl = 0∞ λlφl(r) with λ = J(J + 1). The radial Schrödinger equation can be written (Hv + λHJ)ψvλ = (Ev + Σl = 1∞ λlεl)ψvλ, where ε1, ε2, ε3,… stand for the rotational constants Bv, Dv, Hv,…. The radial equation being satisfied for any value of λ, the rotation “harmonics” φ1, φ2,… are found to be the solutions of a set of inhomogenous differential equations of the form Hφl = Evφl + fl(r)ψv. An analytic expression of the harmonics φi is given for any potential. The numerical application shows that, for a given r, the harmonics decrease in absolute values like Bv, Dv, Hv,… and that the agreement between the values of ψvJ deduced from the computation of the harmonics on one hand, and the direct computation on the other hand, is very satisfactory.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560220104
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