首页> 外文期刊>The Journal of Chemical Physics >Combining coupled cluster and perturbation theory
【24h】

Combining coupled cluster and perturbation theory

机译:结合耦合簇和摄动理论

获取原文
获取原文并翻译 | 示例
           

摘要

Single reference coupled cluster (CC) singles and doubles theory is combined with low-order perturbation theory (PT) to treat ground state electron correlation. Two variants of the general scheme are discussed that differ in the type of amplitudes that are approximated perturbatively and which are treated to infinite order. The combined CC/PT methods to include ground state correlation are merged with equation-of-motion (EOM) and similarity transformed EOM methods to describe excitation spectra of the highly correlated s-tetrazine, MnO_4~- and Ni(CO)_4 systems. It is shown that the computationally efficient CC/PT schemes can reproduce full CCSD results even if perturbation theory by itself is a very poor approximation, as is the case for many transition metal compounds. In a second test CC/PT is applied to determine ground state equilibrium molecular structures and harmonic vibrational frequencies for a set of small molecules. Using either variant of CC/PT, full CCSD geometries are easily recovered, while vibrational frequencies can be more sensitive to details of the approximation.
机译:单参考耦合簇(CC)单打和双打理论与低阶摄动理论(PT)相结合,以处理基态电子相关性。讨论了通用方案的两个变体,它们的振幅类型不同,它们被微扰地近似并且被处理为无穷大。将包括基态相关性的组合CC / PT方法与运动方程(EOM)和相似度转换后的EOM方法合并,以描述高度相关的s-四嗪,MnO_4〜和Ni(CO)_4系统的激发光谱。结果表明,即使扰动理论本身是非常差的近似值,对于许多过渡金属化合物而言,计算有效的CC / PT方案也可以重现全部CCSD结果。在第二项测试中,CC / PT用于确定一组小分子的基态平衡分子结构和谐波振动频率。使用CC / PT的任一变体,都可以轻松恢复完整的CCSD几何形状,而振动频率可能对近似细节更为敏感。

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