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DFT , DLPNO‐CCSD (T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine
Author(s) -
Chamkin Aleksandr A.,
Serkova Elena S.
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26398
Subject(s) - counterpoise , density functional theory , chemistry , trimethylphosphine , valence (chemistry) , perturbation theory (quantum mechanics) , coupled cluster , computational chemistry , physics , quantum mechanics , molecule , basis set , organic chemistry
The reaction between ferrocenium and trimethylphosphine was studied using density functional theory (DFT), domain‐based local pair natural orbital coupled cluster theory with single‐, double‐, and perturbative triple excitations (DLPNO‐CCSD(T)), and N‐electron valence state perturbation theory (NEVPT2). The accuracy of the DFT functionals decreases compared to the DLPNO‐CCSD(T) level in the following order: M06‐L > TPSS > M06, BLYP > PBE, PBE0, B3LYP > > PWPB95 > > DSD‐BLYP. The roles of thermochemical, continuum solvation (SMD), and counterpoise corrections were evaluated. Grimme's D3 empirical dispersion correction is essential for all functionals studied except M06 and M06‐L. The reliability of the frequency calculations performed directly within the SMD was confirmed. The systems showed no significant multireference character according to T 1 and T 2 diagnostics and the fractional occupation number (FOD) weighted electron density analysis. The multireference NEVPT2 calculations gave qualitatively valid conclusions about the reaction mechanism. However, a multireference approach is generally not recommended because it requires arbitrary chosen active spaces.