Analysis of Rotational and Vibrational–Rotational Spectra of HF Based on theNon-Born–Oppenheimer Effective Hamiltonian

摘要

Rotational transitions of HF that are important as a wavenumber standard have been analyzed by simultaneousfitting of the reported rotational and vibrational-rotational transitions plus rotational measurements of thepresent study with the non-Born-Oppenheimer effective Hamiltonian expressed with the optimal parameters,i.e., the determinable clusters of the expansion coefficients of the correction functions for the breakdown ofthe Born-Oppenheimer approximation. Since the spectral fit is made with the analytical solution of theSchrodinger equation, one can easily reproduce the fitting procedure. This is the first example of the non-Born-Oppenheimer analysis of a single isotopologue with physically meaningful parameters based on thetraditional concept of the molecular constants. Fitting of a data set for HF has generated 15 independentparameter values that include 4 determinable clusters of the expansion coefficients. These 15 parameters aresufficient to generate 41 Y_(ij) coefficients and 72 rotational constants, which provide comprehensive sets ofmolecular constants of HF.