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The CuC bond dissociation energy of CuCH3. A dramatic failure of the QCISD(T) method

✍ Scribed by Marlis Böhme; Gernot Frenking

Publisher
Elsevier Science
Year
1994
Tongue
English
Weight
275 KB
Volume
224
Category
Article
ISSN
0009-2614

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✦ Synopsis

The copper-carbon bond dissociation energy of CuCH3 is calculated using coupled cluster (CC) theory and the quadratic CI approach (QCI) in conjunction with an effective core potential (ECP) for Cu. The results at the CCSD (D©=45.4 kcal/mol) and CCSD (T) level (De = 48.0 kcal/mol) are in good agreement with previous high-level calculations using the MCPF approach (De=48.4 kcal/mol). The theoretically predicted dissociation energy at the QCISD(T) level shows a dramatic failure of the estimate for the triple excitations in CuCH3. The QCISD value is De=55.4 kcal/mol, the QCISD(T) values is De=6.0 kcal/ tool. The QCISD(T) method predicts clearly different dissociation energies when the core electrons are explicitly included in the calculations, while the CCSD(T) method gives similar results to the ECP calculations. The predicted dissociation energy using a large all-electron basis set is Dc=52.7 kcal/mol at QCISD and De=29.4 kcal/mol at QCISD(T). The CCSD method gives with the same basis set Dc=46.0 kcal/mol; the value at CCSD (T) is De=49.7 kcal/mol.

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