A simple method for the derivation of exact quantum-mechanical vibration–rotation Hamiltonians in terms of internal coordinates

Lukka, Tuomas J.
March 1995
Journal of Chemical Physics;3/8/1995, Vol. 102 Issue 10, p3945
Academic Journal
By considering infinitesimal rotations, the well-known G-matrix method is extended for the derivation of exact quantum-mechanical vibration–rotation Hamiltonians in arbitrary vibrational coordinates and molecule-fixed coordinate systems. All rovibrational coefficients can be calculated by dot products, with considerably less algebra than by using conventional methods. Coordinate transformations from one molecule-fixed coordinate system to another are discussed. Hamiltonians are partly derived for XH2 and XH3 (without inversion) type molecules to demonstrate the ease of this approach. © 1995 American Institute of Physics.


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