TY - JOUR
T1 - Explicitly correlated coupled cluster benchmarks with realistic-sized ligands for some late-transition metal reactions
T2 - basis sets convergence and performance of more approximate methods
AU - Kesharwani, Manoj K.
AU - Martin, Jan M. L.
N1 - Lise Meitner-Minerva Center for Computational Quantum Chemistry; Helen and Martin A. Kimmel Center for Molecular DesignJ.M.L.M. is the Thatcher Professor of Chemistry at the Weizmann Institute of Science and a member ad personam of the Lise Meitner-Minerva Center for Computational Quantum Chemistry. The authors would like to thank Dr. Brina Brauer for assistance with the M11 calculations, Drs. Irena Efremenko (Weizmann) and Sebastian Kozuch (U. of North Texas) for helpful discussions, and Dr. Mark Vilensky for technical assistance with the Faculty of Chemistry computing cluster. This research was partially supported by the Lise Meitner-Minerva Center for Computational Quantum Chemistry as well as by the Helen and Martin A. Kimmel Center for Molecular Design.
PY - 2014/3/1
Y1 - 2014/3/1
N2 - CCSD(T)-F12b benchmark calculations have been performed for the energetics and barrier heights of three late-transition metal systems, in increasing order of size: oxidative additions at bare Pd, a model for the Grubbs catalyst, and competitive CC/CH activation by a Rh(PCP) pincer complex. The results depend weakly on the basis set on the main-group atoms but are rather more sensitive to the basis set on the metal. An aug-cc-pwCVTZ-PP set on the metal combined with cc-pVTZ-F12 on the main-group elements yields barriers that are effectively converged in the basis set, but even the combination with aug-cc-pwCVTZ-PP on the metal and cc-pVDZ-F12 on the main group, or of def2-TZVPP on the metal and def2-TZVP on the main group, works well enough for most benchmark purposes. Inner-shell correlation cannot be neglected for even semi-accurate work. Simple nonempirical (meta-)GGAs with D3BJ dispersion work quite well for the Grubbs and pincer cases but break down for the Pd example, which requires exact exchange. Hybrids of these same functionals, such as PBE0, TPSS0, and B3PW91, are among the best performers through rung four on Perdew’s ladder. For the Grubbs case, dispersion is very important and D3BJ clearly is superior over D2. Only the DSD double hybrids consistently perform well in the absence of dispersion corrections.
AB - CCSD(T)-F12b benchmark calculations have been performed for the energetics and barrier heights of three late-transition metal systems, in increasing order of size: oxidative additions at bare Pd, a model for the Grubbs catalyst, and competitive CC/CH activation by a Rh(PCP) pincer complex. The results depend weakly on the basis set on the main-group atoms but are rather more sensitive to the basis set on the metal. An aug-cc-pwCVTZ-PP set on the metal combined with cc-pVTZ-F12 on the main-group elements yields barriers that are effectively converged in the basis set, but even the combination with aug-cc-pwCVTZ-PP on the metal and cc-pVDZ-F12 on the main group, or of def2-TZVPP on the metal and def2-TZVP on the main group, works well enough for most benchmark purposes. Inner-shell correlation cannot be neglected for even semi-accurate work. Simple nonempirical (meta-)GGAs with D3BJ dispersion work quite well for the Grubbs and pincer cases but break down for the Pd example, which requires exact exchange. Hybrids of these same functionals, such as PBE0, TPSS0, and B3PW91, are among the best performers through rung four on Perdew’s ladder. For the Grubbs case, dispersion is very important and D3BJ clearly is superior over D2. Only the DSD double hybrids consistently perform well in the absence of dispersion corrections.
UR - http://www.scopus.com/inward/record.url?scp=84893203923&partnerID=8YFLogxK
U2 - 10.1007/s00214-014-1452-2
DO - 10.1007/s00214-014-1452-2
M3 - مقالة
SN - 1432-881X
VL - 133
SP - 1
EP - 14
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 3
M1 - 1452
ER -