在6-311+G~*基组水平上用CISD(configuration interaction with singly and doubly excited configurations)方法研究HX(X=Li-F,HBe^+,HBe)体系电子对内、对间的相关能.计算结果表明不同元素形成的HX(X=Li-F,HBe^+,HBe)体系,其价层电子...在6-311+G~*基组水平上用CISD(configuration interaction with singly and doubly excited configurations)方法研究HX(X=Li-F,HBe^+,HBe)体系电子对内、对间的相关能.计算结果表明不同元素形成的HX(X=Li-F,HBe^+,HBe)体系,其价层电子对内、对间相关能的变化较大,它们之间存在着轨道差别,不宜将其相关贡献归为简单的常数.在使用相同理论方法和相同质量基组的前提下,电子数将直接影响到电子对间相关能的大小.对于多电子体系,电子对间相关在总相关中占有优势,若将其忽略会引起较大误差.展开更多
The proton-transfer between ammonia/water and HF/HBr without and with the stimulus of external electric fields（Eext） was investigated with the ab initio calculations. When external electric field is applied, the pro...The proton-transfer between ammonia/water and HF/HBr without and with the stimulus of external electric fields（Eext） was investigated with the ab initio calculations. When external electric field is applied, the proton transfer occurs, resulting in ion-paired HaN＋X- and H30＋X-（X--Br and F） from hydrogen-bonded complexes in view of the great changes of geometrical structures, dipole moments, frontier molecular orbitals and potential energy surfaces in the critical external electric fields（Ec） of 1.131 × 107 V/cm for H3N-HBr, 1.378× 108 V/cm for H3N-HF, 9.358×107 V/cm for H2O-HBr and 2.304×108 V/cm for H2O-HF, respectively. Furthermore, one or three excess electrons can trigger the proton transfer from H3N-HBr and H3N-HF to HaN＋Br- and H4N＋F-, while two and four excess electrons can induce the proton transfer from H2O-HBr and H2O-HF to H3O＋Br- and H30＋F-, respectively. Compared with that of the analogous NH3/H2O-HC1 systems, the strength of Ec of proton transfer increases from HBr to HCL and HF for either H3N-HX or H2O-HX series, which is understandable by the fact that the acidity sequence is HBr〉HCI〉HF. And the larger of acidity of conjugated acid, the smaller of needed Ec. On the other hand, the Ec for the systems of NH3 with a stronger basicity is generally smaller than that of H2O systems for the same con- jugated acid.展开更多
文摘在6-311+G~*基组水平上用CISD(configuration interaction with singly and doubly excited configurations)方法研究HX(X=Li-F,HBe^+,HBe)体系电子对内、对间的相关能.计算结果表明不同元素形成的HX(X=Li-F,HBe^+,HBe)体系,其价层电子对内、对间相关能的变化较大,它们之间存在着轨道差别,不宜将其相关贡献归为简单的常数.在使用相同理论方法和相同质量基组的前提下,电子数将直接影响到电子对间相关能的大小.对于多电子体系,电子对间相关在总相关中占有优势,若将其忽略会引起较大误差.
基金the Natural Science Foundation of Guangdong Province of China（No.S2013010014476） and the Engagement Fund of Shantou University, China（No.NFC 13001）.
文摘The proton-transfer between ammonia/water and HF/HBr without and with the stimulus of external electric fields（Eext） was investigated with the ab initio calculations. When external electric field is applied, the proton transfer occurs, resulting in ion-paired HaN＋X- and H30＋X-（X--Br and F） from hydrogen-bonded complexes in view of the great changes of geometrical structures, dipole moments, frontier molecular orbitals and potential energy surfaces in the critical external electric fields（Ec） of 1.131 × 107 V/cm for H3N-HBr, 1.378× 108 V/cm for H3N-HF, 9.358×107 V/cm for H2O-HBr and 2.304×108 V/cm for H2O-HF, respectively. Furthermore, one or three excess electrons can trigger the proton transfer from H3N-HBr and H3N-HF to HaN＋Br- and H4N＋F-, while two and four excess electrons can induce the proton transfer from H2O-HBr and H2O-HF to H3O＋Br- and H30＋F-, respectively. Compared with that of the analogous NH3/H2O-HC1 systems, the strength of Ec of proton transfer increases from HBr to HCL and HF for either H3N-HX or H2O-HX series, which is understandable by the fact that the acidity sequence is HBr〉HCI〉HF. And the larger of acidity of conjugated acid, the smaller of needed Ec. On the other hand, the Ec for the systems of NH3 with a stronger basicity is generally smaller than that of H2O systems for the same con- jugated acid.
