Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82–
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 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.
- Authors:
-
- Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Supercomputing Inst.
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1370937
- Grant/Contract Number:
- SC0012702
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Theory and Computation
- Additional Journal Information:
- Journal Volume: 11; Journal 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; Journal ID: ISSN 1549-9618
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 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
Citation Formats
Carlson, Rebecca K., Truhlar, Donald G., and Gagliardi, Laura. Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82–. United States: N. p., 2015.
Web. doi:10.1021/acs.jctc.5b00609.
Carlson, Rebecca K., Truhlar, Donald G., & Gagliardi, Laura. Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82–. United States. https://doi.org/10.1021/acs.jctc.5b00609
Carlson, Rebecca K., Truhlar, Donald G., and Gagliardi, Laura. Fri .
"Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82–". United States. https://doi.org/10.1021/acs.jctc.5b00609. https://www.osti.gov/servlets/purl/1370937.
@article{osti_1370937,
title = {Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82–},
author = {Carlson, Rebecca K. and Truhlar, Donald G. and Gagliardi, Laura},
abstractNote = {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.},
doi = {10.1021/acs.jctc.5b00609},
journal = {Journal of Chemical Theory and Computation},
number = 9,
volume = 11,
place = {United States},
year = {Fri Jul 24 00:00:00 EDT 2015},
month = {Fri Jul 24 00:00:00 EDT 2015}
}
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