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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Energy Barriers in the Conversion of Bicyclobutane to gauche-1,3-Butadiene from the Anti-Hermitian Contracted Schrodinger Equation
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Energy Barriers in the Conversion of Bicyclobutane to gauche-1,3-Butadiene from the Anti-Hermitian Contracted Schrodinger Equation

机译：反赫米特收缩薛定inger方程将双环丁烷转化为gauche-1,3-丁二烯的能垒

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摘要

In 1959 Charles Coulson popularized the idea of computing a molecule's ground-state energy as a functional of the two-electron reduced density matrix(2-RDM)without the many-electron wave function.For 50 years,however,a practical,direct calculation of the 2-RDM was not achieved because the 2-RDM must be constrained by N-representability conditions to represent an N-electron system.Recently,two general approaches to the direct calculation of the 2-RDM have emerged including the solution of the anti-Hermitian contracted Schrodinger equation(ACSE)[Mazziotti,Phys.Rev.Lett.,2006,97,143002].In this article,after further extending the theoretical development of the ACSE method for multireference correlation,we apply the ACSE to studying an unresolved question regarding the opening of bicyclobutane to gauche-1,3-butadiene by conrotatory and disrotatory pathways.Previous theoretical values for the disrotatory energy barrier reveal a disagreement between correlation methods on the order of 10 kcal/mol.By capturing significantly more correlation energy than traditional multireference methods,the ACSE provides new insight into this discrepancy.The ACSE energy for the conrotatory energy barrier agrees with the 40.6 ± 2.5 kcal/mol experimental value.
机译：1959年，查尔斯·库尔森（Charles Coulson）普及了将分子的基态能量计算为不带多电子波函数的双电子降密度矩阵（2-RDM）的功能的想法。然而，50年来，一种实用的直接计算方法由于必须通过N可表示性条件约束2-RDM才能表示N电子系统，因此未能实现2-RDM的线性化。最近，出现了两种直接计算2-RDM的通用方法，包括反Hermitian收缩Schrodinger方程（ACSE）[Mazziotti，Phys.Rev.Lett。，2006,97,143002]。本文在进一步扩展ACSE多参考相关方法的理论发展之后，将ACSE应用于研究关于双环丁烷通过旋流和旋流途径向gauche-1,3-丁二烯开放的尚未解决的问题。旋流能垒的先前理论值揭示了相关方法之间的差异约为10 kca l / mol。ACSE通过捕获比传统的多参考方法更多的相关能量，为这种差异提供了新的见解。用于旋转能垒的ACSE能量与40.6±2.5 kcal / mol实验值相符。

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