Pseudopotential-Based Correlation Consistent Composite Approach (rp-ccCA) for First- and Second-Row Transition Metal Thermochemistry.
Pseudopotential-Based Correlation Consistent Composite Approach (rp-ccCA) for First- and Second-Row Transition Metal Thermochemistry.
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用于第一行和第二行过渡金属热化学的基于赝势的相关一致复合方法 (rp-ccCA)。
DOI：
10.1021/acs.jpca.5b02433
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
A. Wilson
中科院分区：
文献类型：
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作者：
S. Manivasagam;Marie L. Laury;A. Wilson
采用相对论-伪势相关一致复合方法（rp-ccCA）测定了24个第一排（3d）过渡金属化合物的生成焓（ΔHf）。rp- ccca衍生的ΔHf’s与先前用过渡金属（ccCA-TM）的全电子复合方法获得的ΔHf’s进行了比较。对于3d金属体系，rp-ccCA总体上实现了过渡金属精度，在3 kcal/mol的可靠实验数据范围内。通过在rp-ccCA方法中使用伪势，我们观察到与ccCA-TM中使用的全电子基集相比，计算时间节省了53%。利用rp-ccCA的可靠性和准确性，采用该方法构建了210个第二行（4d）过渡金属化合物及其ΔHf's的校准集。四维校准集称为4dHf-210。在4dHf-210集合中，有61个分子具有可用的实验数据。排除异常值（共10个），rp-ccCA的平均实验不确定度为4.05 kcal/mol，平均绝对偏差为3.64 kcal/mol。这项研究提供了大量的能量学，可以用来衡量现有和未来的计算方法，并帮助实验人员进行反应设计。
The relativistic-pseudopotential correlation consistent composite approach (rp-ccCA) was used to determine the enthalpy of formation (ΔHf) of 24 first row (3d) transition metal compounds. The rp-ccCA-derived ΔHf's were compared to ΔHf's previously obtained with an all-electron composite method for transition metals (ccCA-TM). For the 3d metal systems, rp-ccCA achieves transition metal accuracy, within 3 kcal/mol of reliable experimental data, overall. By utilizing pseudopotentials within the rp-ccCA methodology, we observed a significant computational time savings (53%) in comparison to the all-electron basis sets employed within ccCA-TM. With the proven reliability and accuracy of rp-ccCA, the methodology was employed to construct a calibration set of 210 second-row (4d) transition metal compounds and their ΔHf's. The 4d calibration set is referred to as 4dHf-210. Within the 4dHf-210 set, there were 61 molecules with available experimental data. The average experimental uncertainty was 4.05 kcal/mol and the mean absolute deviation of rp-ccCA was 3.64 kcal/mol, excluding outliers (10 total). This study provides a large set of energetics that can be used to gauge existing and future computational methodologies and to aid experimentalists in reaction design.
评估 CCSD 和 CCSD(T) 耦合簇方法在计算 Zn 配合物的生成热时的效果。
DOI：
10.1021/jp904241v
发表时间：
2009
期刊：
The journal of physical chemistry. A
影响因子：
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作者：
Weaver,MichaelN;Yang,Yue;MerzJr,KennethM
通讯作者：
MerzJr,KennethM