Incremental CCSD(T)(F12*)|MP2: A Black Box Method To Obtain Highly Accurate Reaction Energies

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• 作者：Joachim Friedrich ; Julia H盲nchen
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2013
• 出版时间：December 10, 2013
• 年：2013
• 卷：9
• 期：12
• 页码：5381-5394
• 全文大小：475K
• 年卷期：v.9,no.12(December 10, 2013)
• ISSN：1549-9626

文摘

In this work we present a new partitioning scheme for the incremental approach in combination with the efficient (F12*) approximation for explicitly correlated coupled cluster (J. Chem. Phys. 2010, 132, 231102). Furthermore we establish a black-box truncation scheme which provides chemical accuracy for the absolute energies of 81 molecules and 51 reaction energies. The errors in the absolute CCSD(T)/cc-pVTZ-F12 energies due to the local approximations are characterized by mean = 鈭?.24 kJ/mol, 蟽 = 0.49 kJ/mol, mae = 0.37 kJ/mol, rmsd = 0.54 kJ/mol, and range = 3.63 kJ/mol. For the reaction energies we find mean = 0.07 kJ/mol, 蟽 = 0.49 kJ/mol, mae = 0.33 kJ/mol, rmsd = 0.49 kJ/mol, and range = 2.40 kJ/mol. On the basis of these findings it is evident that the incremental scheme provides highly accurate CCSD(T) energies of benchmark quality.