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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 Re2Cl82–

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Supercomputing Inst.
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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 Cr2, Cu2, Ag2, Os2, and Re2Cl82– 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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012702
OSTI ID:
1370937
Journal Information:
Journal of Chemical Theory and Computation, Vol. 11, Issue 9; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 86 works
Citation information provided by
Web of Science

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Cited By (13)

Scaling exchange and correlation in the on-top density functional of multiconfiguration pair-density functional theory: effect on electronic excitation energies and bond energies journal January 2020
Separated-pair approximation and separated-pair pair-density functional theory journal January 2016
Excitation spectra of retinal by multiconfiguration pair-density functional theory journal January 2018
How well can density functional theory and pair-density functional theory predict the correct atomic charges for dissociation and accurate dissociation energetics of ionic bonds? journal January 2018
Density matrix renormalization group pair-density functional theory (DMRG-PDFT): singlet–triplet gaps in polyacenes and polyacetylenes journal January 2019
State-interaction pair density functional theory for locally avoided crossings of potential energy surfaces in methylamine journal January 2019
Communication: Towards ab initio self-energy embedding theory in quantum chemistry journal December 2015
MC-PDFT can calculate singlet–triplet splittings of organic diradicals journal February 2018
On-top density functionals for the short-range dynamic correlation between electrons of opposite and parallel spin journal April 2018
State-interaction pair-density functional theory journal July 2018
Range-separated multideterminant density-functional theory with a short-range correlation functional of the on-top pair density journal February 2019
Ground-state actinide chemistry with scalar-relativistic multiconfiguration pair-density functional theory journal October 2019
Density matrix renormalization group pair-density functional theory (DMRG-PDFT): singlet-triplet gaps in polyacenes and polyacetylenes text January 2019

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Related Subjects

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