Dynamically weighted multiconfiguration self-consistent field:: Multistate calculations for F+H2O→HF+OH reaction paths
Dynamically weighted multiconfiguration self-consistent field:: Multistate calculations for F+H2O→HF+OH reaction paths
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DOI：
10.1063/1.1667468
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发表时间：
2004-04-22
影响因子：
4.4
通讯作者：
Werner, HJ
中科院分区：
文献类型：
--
作者：
Deskevich, MP;Nesbitt, DJ;Werner, HJ
提出了一种适用于任意维系统的状态平均多构型自洽场计算（SA-MCSCF）中动态调整权重因子的新方法。提出的动态加权方法自动对势能面各个区域的相关电子态进行加权，并利用能量依赖泛函在这些区域之间进行平滑调整。该方法在F(P-2)+H2O—>HF+OH（(2)Pi）反应上进行了测试，由于(i)反应物（三倍）和生成物（两倍）通道的渐近简并不同，以及（ii）在过渡态区域附近存在低电荷转移构型，因此用传统的SA-MCSCF方法描述该反应具有挑战性。动态加权多构型自洽场得到的光滑变化波函数为高阶多构型相互作用计算提供了良好的参考状态，为构建多态势能面提供了理想的起点。(C) 2004年美国物理研究所。
A novel method of dynamically adjusted weighting factors in state-averaged multiconfiguration self-consistent-field calculations (SA-MCSCF) is described that is applicable to systems of arbitrary dimensionality. The proposed dynamically weighted approach automatically weights the relevant electronic states in each region of the potential energy surface, smoothly adjusting between these regions with an energy dependent functional. This method is tested on the F(P-2)+H2O-->HF+OH((2)Pi) reaction, which otherwise proves challenging to describe with traditional SA-MCSCF methods due to (i) different asymptotic degeneracies of reactant (threefold) and product (twofold) channels, and (ii) presence of low-lying charge transfer configurations near the transition state region. The smoothly varying wave functions obtained by dynamically weighted multiconfigurational self-consistent field represent excellent reference states for high-level multireference configuration interaction calculations and offer an ideal starting point for construction of multiple state potential energy surfaces. (C) 2004 American Institute of Physics.