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Title: Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes

Abstract

The applicability of ab initio multireference wavefunction-based methods to the study of magnetic complexes has been restricted by the quickly rising active-space requirements of oligonuclear systems and dinuclear complexes with S > 1 spin centers. Ab initio density matrix renormalization group (DMRG) methods built upon an efficient parameterization of the correlation network enable the use of much larger active spaces, and therefore may offer a way forward. Here, we apply DMRG-CASSCF to the dinuclear complexes [Fe{sub 2}OCl{sub 6}]{sup 2−} and [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+}. After developing the methodology through systematic basis set and DMRG M testing, we explore the effects of extended active spaces that are beyond the limit of conventional methods. We find that DMRG-CASSCF with active spaces including the metal d orbitals, occupied bridging-ligand orbitals, and their virtual double shells already capture a major portion of the dynamic correlation effects, accurately reproducing the experimental magnetic coupling constant (J) of [Fe{sub 2}OCl{sub 6}]{sup 2−} with (16e,26o), and considerably improving the smaller active space results for [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+} with (12e,32o). For comparison, we perform conventional MRCI+Q calculations and find the J values to be consistent with those from DMRG-CASSCF. In contrast to previous studies, the highermore » spin states of the two systems show similar deviations from the Heisenberg spectrum, regardless of the computational method.« less

Authors:
;  [1]; ;  [2]
  1. Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan)
  2. Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585 (Japan)
Publication Date:
OSTI Identifier:
22255172
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 5; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMMONIA; CHROMIUM COMPLEXES; COUPLING CONSTANTS; DENSITY MATRIX; HIGH SPIN STATES; IRON; LIGANDS; RENORMALIZATION; SPECTRA; WAVE FUNCTIONS

Citation Formats

Harris, Travis V., Morokuma, Keiji, E-mail: morokuma@fukui.kyoto-u.ac.jp, Kurashige, Yuki, and Yanai, Takeshi. Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes. United States: N. p., 2014. Web. doi:10.1063/1.4863345.
Harris, Travis V., Morokuma, Keiji, E-mail: morokuma@fukui.kyoto-u.ac.jp, Kurashige, Yuki, & Yanai, Takeshi. Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes. United States. doi:10.1063/1.4863345.
Harris, Travis V., Morokuma, Keiji, E-mail: morokuma@fukui.kyoto-u.ac.jp, Kurashige, Yuki, and Yanai, Takeshi. 2014. "Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes". United States. doi:10.1063/1.4863345.
@article{osti_22255172,
title = {Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes},
author = {Harris, Travis V. and Morokuma, Keiji, E-mail: morokuma@fukui.kyoto-u.ac.jp and Kurashige, Yuki and Yanai, Takeshi},
abstractNote = {The applicability of ab initio multireference wavefunction-based methods to the study of magnetic complexes has been restricted by the quickly rising active-space requirements of oligonuclear systems and dinuclear complexes with S > 1 spin centers. Ab initio density matrix renormalization group (DMRG) methods built upon an efficient parameterization of the correlation network enable the use of much larger active spaces, and therefore may offer a way forward. Here, we apply DMRG-CASSCF to the dinuclear complexes [Fe{sub 2}OCl{sub 6}]{sup 2−} and [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+}. After developing the methodology through systematic basis set and DMRG M testing, we explore the effects of extended active spaces that are beyond the limit of conventional methods. We find that DMRG-CASSCF with active spaces including the metal d orbitals, occupied bridging-ligand orbitals, and their virtual double shells already capture a major portion of the dynamic correlation effects, accurately reproducing the experimental magnetic coupling constant (J) of [Fe{sub 2}OCl{sub 6}]{sup 2−} with (16e,26o), and considerably improving the smaller active space results for [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+} with (12e,32o). For comparison, we perform conventional MRCI+Q calculations and find the J values to be consistent with those from DMRG-CASSCF. In contrast to previous studies, the higher spin states of the two systems show similar deviations from the Heisenberg spectrum, regardless of the computational method.},
doi = {10.1063/1.4863345},
journal = {Journal of Chemical Physics},
number = 5,
volume = 140,
place = {United States},
year = 2014,
month = 2
}
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