Accurate thermochemistry for molecules containing heavy p-block elements using local explicitly correlated ab initio methods

使用局部显式相关的从头计算方法对含有重 p 区元素的分子进行准确的热化学分析

• 批准号: 52486322
• 负责人: Professor Dr. Hans-Joachim Werner
• 金额: --
• 依托单位: Institut für Theoretische Chemie (ITheoC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2007
• 资助国家: 德国
• 起止时间: 2006-12-31 至 2011-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/52486322?language=en
• 关键词: Accurate; thermochemistry; molecules; containing; heavy

Over the last years it has been demonstrated that accurate ab initio methods can predict thermochemical data with an uncertainty of 1-4 kJ/mol, which is often more accurate than experimental values. However, so far this is restricted to very small molecules containing first and second row atoms only. The aim of the present proposal is to extend this methodology to the remainder of the heavier p-block elements and larger molecules. The novel aspects of this work are fourfold: (i) newly developed explicitly correlated methods (MP2-F12 and CCSD(T)-F12) will be utilitized to minimize the substantial errors that can arise from the slow convergence of the 1-particle basis sets. (ii) Scalar and spin-orbit relativistic effects, which are of crucial importance in these systems, will be recovered using carefully benchmarked relativistic effective core potentials (ECPs). New systematically convergent basis sets for F12 methods in conjunction with ECPs will be developed as part of the work. (iii) Local correlation methods will be used for larger systems. (iv) Analytical energy gradients will be implemented for MP2-F12 and CCSD(T)-F12 methods.

在过去的几年里，已经证明，准确的从头算方法可以预测热化学数据的不确定性为1-4 kJ/mol，这往往是更准确的实验值。然而，到目前为止，这仅限于包含第一和第二行原子的非常小的分子。本提案的目的是将这种方法扩展到其余较重的p区元素和较大分子。这项工作的新方面是四个方面：（i）新开发的显式相关方法（MP2-F12和CCSD（T）-F12）将被用来最大限度地减少由于1粒子基组的缓慢收敛而产生的实质性误差。(ii)标量和自旋轨道相对论效应，这是至关重要的，在这些系统中，将恢复使用仔细基准的相对论有效的核心潜力（ECP）。作为工作的一部分，将开发F12方法与ECPs结合的新的系统收敛基组。(iii)局部相关方法将用于较大的系统。(iv)将对MP2-F12和CCSD（T）-F12方法实施分析能量梯度。

项目成果

Explicitly correlated coupled cluster methods with pair-specific geminals

• DOI: 10.1080/00268976.2010.526641
• 发表时间: 2011-02
• 期刊: Molecular Physics
• 影响因子: 1.7
• 作者: H. Werner;G. Knizia;F. Manby

Application of explicitly correlated coupled-cluster methods to molecules containing post-3d main group elements

显式相关耦合簇方法在包含后 3d 主族元素的分子中的应用

• DOI: 10.1080/00268976.2011.624129
• 发表时间: 2011
• 期刊: Molecular Physics
• 影响因子: 1.7
• 作者: K. A. Peterson;C. Krause;H. Stoll;J. G. Hill;H.-J. Werner
• 通讯作者: H.-J. Werner