The importance of three-body terms in the fragment molecular orbital method

摘要

A previously proposed two-body fragment molecular orbital method based on the restricted Hartree-Fock (RHF) method was extended to include explicit three-body terms.The accuracy of the method was tested on a set of representative molecules:(H_2O)_n,n=16,32,and 64,as well as a and beta n-mers of alanine,n = 10,20,and 40,using STO-3G,3-21G,6-31G,and 6-31++G~** basis sets.Two- and three-body results are presented separately for assigning one and two molecules(or residues) per fragment.Total energies are found to differ from the regular RHF method by at most DELTAE_2/1=0.06,DELTAE_2/2=0.04,DELTAE_3/1=0.02,and DELTAE_3/2=0.003(a.u.);rms energy gradients differ by at most DELTAG_2/1=0.0015,DELTAG_2/2=0.000 75,DELTAG_3/1=0.00020,and deltaG3/2=0.000 10(a.u./bohr),and rms dipole moments are reproduced with at most deltaD2/1=3.7,deltaD_2/2=3.4,deltaD_3/1=2.6,and deltaD_3/2=3.1(%)relative error,where the subscript notation n/m refers to the n-body method based on m molecules(residues)per fragment.A few of the largest three-body calculations were performed with a separated trimer approximation,which presumably somewhat lowered the accuracy of mostly dipole moments which are very sensitive to slight variations in the density distribution.The proposed method is capable of providing sufficient chemical accuracy while providing detailed information on many-body interactions.