共查询到19条相似文献,搜索用时 218 毫秒
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通过MELD程序MP2-OPT2方法在6-311++G(d)及6-311++G(3df, 3pd)基组下对KX(X = OH, NC)体系对内对间电子相关能的计算结果和分析, 并根据KX(X = OH, NC)分子中K和X组分的内层电子对相关能和内层电子相关效应的传递性, 定义并且计算了Kδ +和Kδ -对KX分子体系的电子相关能贡献. 基于K+, X-和KX(X = OH, NC)的对相关能的比较结果, 提出了利用其组成金属离子和负离子基团的电子相关能之和来计算多原子强离子键分子体系电子相关能的简单计算方法, 此方法对Gaussian98程序MP2(full)/6-311++G(d)水平下二聚体系(KOH))2和(KNC))2的电子相关能的近似计算结果误差很小, 应用此“化整为零”的方案计算大分子离子键体系电子相关能既可以基本达到化学计算要求的精度又能节约大量的计算工作量. 相似文献
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电子气近似中的电子相关能与量子化学中的Hartree-Fock相关能在定义上不相互等同。作者从假想的、含N个电子的"有限电子气"出发, 通过比较这类体系与无限电子气在物理模型上的差异, 合理地把电子气相关能定量地分解为单电子自相关、电子自旋平行相关以及Hartree-Fock相关三个部分。并阐明了各组分的构成随N的变化规律。在此基础上建立的Hartree-Fock与密函混合处理方案, 无须借助任何经验参数, 仅通过简捷的计算即可实现原子和分子的相关能校正。平均误差为4.2%, 优于CI-SD和MP4等Hartree-Fock处理的结果。 相似文献
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电子气近似中的电子相关能与量子化学中的Hartree-Fock相关能在定义上不相互等同 作者从假想的、含N个电子的“有限电子气”出发,通过比较这类体系与无限电子气在物理模型上的差异,合理地把电子气相关能定量地分解为单电子自相关、电子自旋平行相关以及Hartree-Fock相关三个部分,并阐明了各组分的构成随N的变化规律在此基础上建立的Hartree-Fock与密函混合处理方案,无须借助任何经验参数,仅通过简捷的计算即可实现原子和分子的相关能校正平均误差为4.2%,优于CI—SD和MP_4等Hartree—Fock处理的结果. 相似文献
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在本文中,提出了极性基团电子相关能贡献的定义,并在MP2-OPT2/6-311++G(d)水平上计算了CH3(CH2) mOH( m=0-4)体系中HO-、CH3-和-CH2-基团电子相关能贡献值。计算结果表明,在CH3(CH2) mOH( m=0-4)体系中端基HO-、CH3-基团电子相关能贡献值 Ecorr(HO-)和 Ecorr(cH3-)的数值随着 m的增加而逐渐减小。同一体系中a -CH2-基团电子相关能贡献值大于其它-CH2-基团电子相关能贡献值,在CH3(CH2) mOH( m=1-4)体系中,距离端基HO-基团越远的-CH2-基团其电子相关能贡献值越小;通过计算结果可以推断,在CH3(CH2) mOH体系中随着 m的逐渐增加,相对远离端基HO-的-CH2-基团的电子相关能贡献值表现出收敛趋向并将趋于不变,此-CH2-基团可看作一个标准的亚甲基而且其 Ecorr(-cH2-)的数值在CH3(CH2) mOH体系中具有传递性。在MP2-OPT2/6-311++G(d)水平上对CH3(CH2) mOH( m=2-4)体系的计算结果和应用Gaussian 98程序在MP2/6-311++G(d)//HF/6-311++G(d)水平上对CH3(CH2) mOH( m=2-7)体系的计算结果均表明,体系总电子相关能与( m-1)呈 中 m是体系中亚甲乙烯基的数值。 相似文献
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众所周知,电子相关能问题是量子化学的瓶颈问题‘’‘.为了更深人地了解和认识电子相关能的轨道本质,建立P。St-HF理论校正模型,JS等”-”应用电子对内对间电子相关模式,指出国际著名量子 相似文献
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The intrapair and interpair correlation energies of F-, HF and H2F^ systems are calculated and analyzed using MP2-OPT2 method of MELD program with cc-PVSZ^* basis set. From the analysis of pair correlation energies of these isoelectronlc sysoterns, it is found that the 1sF^2 pair correlation energy is trans-ferable in these three isociectronic systems. According to the definition of pair correlation contribution of one electron pair to a system, the pair correlation contribution values of these three systems are calculated. The correlation contribution values of inner electron pairs and H—F bonding electron pair in HF molecule with those in H2F^ system are compared. The results indicate that the bonding effect of a molecule is one of the im-portant factors to influence electron correlation energy of the system. The comparison of correlation energy contributions in-cluding triple and quadruple excitations with those only includ-ing singles and doubles calculated with 6-311 G(d) basis set shows that the higher.excitation correlation energy contribution gives more than 2 % of the total correlation energy for these sys-tems. 相似文献
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在6-311+G^*基组水平上用CISD(configurationinteractionwithsinglyanddoublyexcitedconfigurations)方法研究HX(X=Li-F,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。 相似文献
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Guan-Zhi Ju Francisco B. C. Machado Ernest R. Davidson 《International journal of quantum chemistry》1995,54(5):299-304
This article reports the intrapair and interpair electron correlation energies of the radical NaCl2. The total interpair correlation energy dominates. Hence, the interpair electron correlation energy must be considered in building models for correcting computed correlation energies. The 6-311+G* basis set recovers only 32% of the total estimated correlation energy and 44% of this amount came from the core electrons. © 1995 John Wiley & Sons, Inc. 相似文献
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According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation energy of K and L shell changes little. It has also been found that in MCI series compounds the value of Cl correlation energy contribution depends on the ionicity of MCI compounds, i.e., the Cl correlation energy contribution increases with the increase of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl" anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic compounds and the energy changes of chemical reactions. 相似文献
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According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation energy of K and L shell changes little. It has also been found that in MCl series compounds the value of Cl correlation energy contribution depends on the ionicity of MCl compounds, i.e., the Cl correlation energy contribution increases with the increase of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl- anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic compounds and the energy changes of chemical reactions. 相似文献
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According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been
found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation
energy of K and L shell changes little. It has also been found that in MCl series compounds the value of Cl correlation energy
contribution depends on the ionicity of MCl compounds, i.e., the Cl correlation energy contribution increases with the increase
of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl- anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic
compounds and the energy changes of chemical reactions. 相似文献
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First, the intrapair and interpair correlation energies of the Rg atom, X atom, and the optimized RgX (Rg = Ar, Kr, X = F, Cl, Br) complexes are calculated by the MELD program at the 6‐311++g(d), 6‐311++g(3df, 3pd), and cc‐pvqz basis sets (denoted by basis sets a, b, and c, respectively). It is found that the relationship Ecorr(RgX) ≈ Ecorr(Rg) + Ecorr(X) is correct for all the above systems but introducing an unsound absolute error for some RgX systems. Second, the same calculations are selectively carried out for ArF (the smallest system) and KrBr (the largest system) at their increasing interatomic distance. It was found that both the correlation energies of ArF and those of KrBr will decrease whenever the interatomic distance of them become larger. On the basis of our results, we provided an approach to quickly estimate the correlation energies of RgX complexes by which not only the absolute error becomes smaller but more computation work is saved than the direct calculation. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 相似文献
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On the basis of the calculations and analyses of the intrapair and interpair correlation energy of KX (X = OH, NC) molecules and the results of the transferability of both the innermost intrapair correlation energy and the inner core effect of K and X in KX molecules, we defined and calculated the Kδ- and Xδ-correlation contributions to the total correlation energy of KX molecules. With the comparison of the pair correlation energy of K+, X- and KX systems, we present a simple estimation method to estimate the electron correlation energy of strong ionic compound by summarizing the correlation energy of its constituent ion and ionic group. By using this simple method, the reasonable estimation results of the correlation energy of (KOH)2 and (KNC)2 have been obtained at mp2/6-311++G(d) level with Gaussian98 program, and the deviations are very small. Applying the scheme of "Separate Large System into Smaller Ones" to the calculation of electron correlation energy of large ionic compounds, it can not only 相似文献
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On the basis of the calculations and analyses of the intrapair and interpair correlation energy of KX (X = OH, NC) molecules and the results of the transferability of both the innermost intrapair correlation energy and the inner core effect of K and X in KX molecules, we defined and calculated the Kδ+ and Xδ-correlation contributions to the total correlation energy of KX molecules. With the comparison of the pair correlation energy of K+, X- and KX systems, we present a simple estimation method to estimate the electron correlation energy of strong ionic compound by summarizing the correlation energy of its constituent ion and ionic group. By using this simple method, the reasonable estimation results of the correlation energy of (KOH)2 and (KNC)2 have been obtained at mp2/6-311++G(d) level with Gaussian98 program, and the deviations are very small. Applying the scheme of “Separate Large System into Smaller Ones” to the calculation of electron correlation energy of large ionic compounds, it can not only save lot of computation work but also reach the chemical accuracy. 相似文献