Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re 2 Cl 8 2–

Carlson, Rebecca K.; Truhlar, Donald G.; Gagliardi, Laura

doi:10.1021/acs.jctc.5b00609

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Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re 2 Cl 8 2–

Carlson, Rebecca K.·Truhlar, Donald G.·Gagliardi, Laura

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Abstract

We extend the on-top density functional of multiconfiguration pair-density functional theory (MC-PDFT) to include the gradient of the on-top density as well as the gradient of the density. We find that the theory is reasonably stable to this extension; furthermore, it provides improved accuracy for molecules containing transition metals. We illustrate the extended on-top density functionals by applying them to Cr 2 , Cu 2 , Ag 2 , Os 2 , and Re 2 Cl 8 2– as well as to our previous database of 56 data for bond dissociation energies, barrier heights, reaction energies, proton affinities, and the water dimer. The performance of MC-PDFT is comparable to or better than that of CASPT2.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY density functional theory dissociation energies multiconfigurational wave function on-top pair density potential energy curves transition metal dimers

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Carlson, Rebecca K., Truhlar, Donald G., Gagliardi, Laura. 2015-07-24. Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re 2 Cl 8 2–. https://doi.org/10.1021/acs.jctc.5b00609

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