Taming the First-Row Diatomics: A Full Configuration Interaction Quantum Monte Carlo Study
Taming the First-Row Diatomics: A Full Configuration Interaction Quantum Monte Carlo Study
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DOI：
10.1021/ct300504f
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发表时间：
2012-11-01
影响因子：
5.5
通讯作者：
Alavi, Ali
中科院分区：
文献类型：
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作者：
Cleland, Deidre;Booth, George H.;Alavi, Ali
引发剂全组态相互作用量子Monte Carlo（i-FCIQMC）方法是近年来发展起来的一种高精度的随机电子结构分析方法。事实证明，它可以计算小分子的精确基组基态能量，误差在适度的随机误差范围内。使用可交易的计算成本。在这里，我们使用这种技术。为了阐明，通常麻烦的一系列第一行图形包括。Be-2、C-2、CN、CO、N-2、NO、O-2和F-2。利用i-FCIQMC，这些分子的离解能得到。几乎完全在化学精确度之内。实验结果此外，i-FCIQMC计算进行。以相对黑盒的方式，没有任何先验知识或波函数的规范。i-FCIQMC的尺寸一致性也被证明与这些化合物在其更多的多构型拉伸的几何形状。割和简单的i-FCIQMC波函数得到这些系统进行了比较和研究，以证明动态识别的主导因素，有助于显着的静态相关性。这种决定因素的外观和性质，提供洞察到的i-FCIQMC算法和的approxics本身。
The initiator full configuration interaction quantum Monte Carlo (i-FCIQMC) method has recently been developed as a highly accurate stochastic electronic structure technique. It has been shown to calculate the exact basis set ground state energy of Small molecules, to within modest stochastic error bars,. using tradable computational cost. Here, we use this technique. to elucidate, an often troublesome series of first row diatomics consisting. of Be-2, C-2, CN, CO, N-2, NO, O-2, and F-2. Using i-FCIQMC, the dissociation energies of these molecules are obtained. almost entirely to within chemical accuracy of. experimental results Furthermore, the i-FCIQMC calculations are performed. in a relatively black box manner, without any a priori knowledge or specification of the Wave function. The Size consistency of i-FCIQMC is also demonstrated with regards to these diatomics at their more multiconfigurational stretched geometries. The cleat and simple i-FCIQMC wave functions obtained for these systems are then compared and investigated to demonstrate the dynamic identification of the dominant determinants contributing to significant static correlation. The appearance and nature of such determinants is shown to provide insight into both the i-FCIQMC algorithm and the diatomics themselves.