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-

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

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41 Citations (Scopus)

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. (Graph Presented)

Original languageEnglish (US)
Pages (from-to)4077-4085
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume11
Issue number9
DOIs
StatePublished - Sep 8 2015

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Dimers
Transition metals
Density functional theory
transition metals
dimers
Spectroscopy
density functional theory
gradients
Energy barriers
approximation
spectroscopy
Protons
Molecules
Water
proton energy
functionals
affinity
dissociation
water
molecules

Cite this

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title = "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-",
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. (Graph Presented)",
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T2 - A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re 2 Cl 8 2-

AU - Carlson, Rebecca K.

AU - Truhlar, Donald G.

AU - Gagliardi, Laura

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N2 - 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. (Graph Presented)

AB - 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. (Graph Presented)

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