Investigation of the use of density functionals in second‐ and third‐row transition metal dimer calculations

Abstract

ABSTRACT:We explore the use of density functionals in calculating the equilibrium distances, dissociation energies, and harmonic vibrational frequencies of the homonuclear diatomics of the second-row transition metals, platinum, and gold. The outermost s-d interconfigurational energies (ICEs) and the outermost s and d ionization potentials (IPs) were also calculated for the second-and third-row transition metal atoms. Keywords: second-and third-row transition metal dimer; BOP functional; dissociation potential well; outermost s and d orbitals; long-range exchange interaction

Transition metal dimers as potential molecular magnets: A challenge to computational chemistry

“…The agreement with other calculations and experimental results is reasonable, and the agreement with calculations performed by Yanagisawa et al 9 is better than with results by Wu. 8 The non-magnetic Ag 2 dimer is excluded from further consideration.…”

“…8,9 Our calculated state with 2S + 1 = 7 lies approximately 400 meV above the ground state. Its structural data agree well with related literature values and also with the experimental vibrational frequency.…”

Principles of Dinitrogen Hydrogenation: Computational Insights

“…However, hybrid density functionals such as B3LYP [57,58] used in our studies overstabilize, while non-hybrid functionals (like BLYP [58,59], PBE [60,61], etc.) understabilize the high-spin states relative to the low-spin states [62][63][64][65][66]. Unfortunately, application of the best approaches for calculating the energy difference between the lowest electronic states, such as CCSD(T) and MRSD-CI with a very large basis sets, to transition metal complexes such as [(h 5 -C 5 Me n H 5Àn ) 2 M] 2 (m 2 ,h 2 ,h 2 -N 2 ) is not practical, yet.…”

Characterization of synthetic oxomanganese complexes and the inorganic core of the O2-evolving complex in photosystem II: Evaluation of the DFT/B3LYP level of theory

“…High-level benchmarks on open-shell transition metal species are much less frequently reported [39]. However, the study of transition metal compounds has been dominated by the well-established BP86 and B3LYP functionals [30,31,35,[62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80], even when the parameterization of such functionals has not included any transition metal compound in the reference data set. Therefore, considering that the electronic structure of transition metal complexes and main group compounds are qualitatively different, it would not be surprising if these functionals were to exhibit important shortcomings in the description of low-lying spin states of open-shell transition-metal complexes [80][81][82][83][84][85].…”