We modified Mulikens overlap population n(A, B)=2∑Bλ∑Aμ∑in_ic~*_A,μic_B,λis_Aμ,Bλ and obtained an experiential formula N(A,B)=N_A(A,B)+N_B(A,B) of judging bond strength, where N_A(A, B)=\{Z_AN^2_A(2∑Bλ∑...We modified Mulikens overlap population n(A, B)=2∑Bλ∑Aμ∑in_ic~*_A,μic_B,λis_Aμ,Bλ and obtained an experiential formula N(A,B)=N_A(A,B)+N_B(A,B) of judging bond strength, where N_A(A, B)=\{Z_AN^2_A(2∑Bλ∑Aμ∑i\}n_ic~*_A,μic_B,λis_Aμ,Bλ), N_B(A, B)=Z_BN^2_B(2∑Bλ∑Aμ∑in_ic~*_A,μic_B,λis_Aμ,Bλ). Twenty-eight bonds calculated by IEHM method and 11 monohydrides calculated by using 6-31G~** basis sets at Hartree-Fock level, electronic correlation effects are also considered through MP2/6-31G~**, were used to verify our experiential formula. Compared with the judgment of chemical bond strength by means of Mulikens overlap population, our experiential formula has a more obvious improvement as a judgment of bond strength than Mulikens overlap population. As a judgment of chemical bond strength between atoms in molecules, the experiential formula has conquered some limitations of Mulikens overlap population, and accorded with the experimental results.展开更多
文摘We modified Mulikens overlap population n(A, B)=2∑Bλ∑Aμ∑in_ic~*_A,μic_B,λis_Aμ,Bλ and obtained an experiential formula N(A,B)=N_A(A,B)+N_B(A,B) of judging bond strength, where N_A(A, B)=\{Z_AN^2_A(2∑Bλ∑Aμ∑i\}n_ic~*_A,μic_B,λis_Aμ,Bλ), N_B(A, B)=Z_BN^2_B(2∑Bλ∑Aμ∑in_ic~*_A,μic_B,λis_Aμ,Bλ). Twenty-eight bonds calculated by IEHM method and 11 monohydrides calculated by using 6-31G~** basis sets at Hartree-Fock level, electronic correlation effects are also considered through MP2/6-31G~**, were used to verify our experiential formula. Compared with the judgment of chemical bond strength by means of Mulikens overlap population, our experiential formula has a more obvious improvement as a judgment of bond strength than Mulikens overlap population. As a judgment of chemical bond strength between atoms in molecules, the experiential formula has conquered some limitations of Mulikens overlap population, and accorded with the experimental results.
基金supported by the National Natural Science Foundation of China(10804027,11011140321)Natural Science Foundation of Education Department of Henan Province,China(2011A140003)~~
