Journal of Chemical Physics, Vol.109, No.21, 9451-9462, 1998
The calculation of accurate O-17 hyperfine coupling constants in the hydroxyl radical : A difficult problem for current quantum chemical methods
The hyperfine coupling constants (HFCCs) in the hydroxyl radical are investigated through comparison of results obtained from a variety of quantum chemical methods. The couplings obtained from the multi-reference configuration interaction (MRCI) wave function, built upon the restricted open-shell Hartree-Fock (ROHF) reference determinant, are investigated in terms of the basis set, the configuration selection energy threshold, and the size of the reference space. Overall results which converge to the experimental couplings are obtained for hydrogen, but not for oxygen. In particular, the MRCI method shows no improvement over density functional theory (the B3LYP functional), for the calculation of A(iso)(O-17). On the other hand, results in excellent agreement with experiment are obtained through the use of the quadratic configuration interaction (QCISD) method based on the unrestricted HF (UHF) reference determinant with the identical basis sets. Examination of UHF and ROHF based coupled-cluster methods, CCSD and CCSD(T), indicates that once a high enough level of electron correlation is included, the oxygen HFCC is independent of the form of the reference determinant. Unlike the ROHF-CCSD method, which yields reliable results once the effects of triple excitations have been taken into account, the MRCI wave function cannot easily be adjusted to account for the inadequacies of the ROHF reference determinant in order to accurately predict O-17 HFCCs.
Keywords:GAUSSIAN-BASIS SETS, MOLECULAR-ORBITAL METHODS, HARTREE-FOCKEXCHANGE, CONFIGURATION-INTERACTION CALCULATIONS, DENSITY-FUNCTIONAL METHODS, MANY-BODY CALCULATIONS, 2ND ROW ATOMS;DIATOMIC-MOLECULES, ORGANIC-MOLECULES, 1ST-ROW HYDRIDES