• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The Journal of Chemical Physics >Configuration interaction based on constrained density functional theory:A multireference method
【24h】

Configuration interaction based on constrained density functional theory:A multireference method

机译：基于约束密度泛函理论的构型相互作用：一种多参考方法

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Existing density functional theory (DFT) methods are typically very effective in capturing dynamic correlation,but run into difficulty treating near-degenerate systems where static correlation becomes important.In this work,we propose a configuration interaction (CI) method that allows one to use a multireference approach to treat static correlation but incorporates DFT's efficacy for the dynamic part as well.The new technique uses localized charge or spin states built by a constrained DFT approach to construct an active space in which the effective Hamiltonian matrix is built.These local configurations have significantly less static correlation compared to their delocalized counterparts and possess an essentially constant amount of self-interaction error.Thus their energies can be reliably calculated by DFT with existing functionals.Using a small number of local configurations as different references in the active space,a simple CI step is then able to recover the static correlation missing from the localized states.Practical issues of choosing configurations and adjusting constraint values are discussed,employing as examples the ground state dissociation curves of H_2~+,H2,and LiF.Excellent results are obtained for these curves at all interatomic distances,which is a strong indication that this method can be used to accurately describe bond breaking and forming processes.
机译：现有的密度泛函理论（DFT）方法通常在捕获动态相关性时非常有效，但是在处理静态相关性很重要的近退化系统时遇到了困难。在这项工作中，我们提出了一种配置相互作用（CI）方法，该方法允许使用这种新技术利用约束DFT方法建立的局部电荷或自旋态来构建活动空间，并在其中构建有效的哈密顿矩阵，从而建立了有效的哈密顿矩阵。与离域的同类相比，它们的静态相关性要低得多，并且具有基本恒定的自交互误差。因此，可以通过DFT使用现有功能可靠地计算其能量。在活动空间中使用少量局部配置作为不同的参考，一个简单的CI步骤就能恢复静态相关性m讨论了选择构型和调整约束值的实际问题，以H_2〜+，H2和LiF的基态解离曲线为例。在所有原子间距离处，这些曲线均获得了优异的结果。有力的迹象表明，该方法可用于准确描述粘结破坏和形成过程。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号