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

Journal Article · Fri Feb 07 04:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4863345· OSTI ID:22255172

Harris, Travis V.; Morokuma, Keiji ^[1]; Kurashige, Yuki; Yanai, Takeshi ^[2]

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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)

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.

• OSTI ID: 22255172
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AMMONIA
CHROMIUM COMPLEXES
COUPLING CONSTANTS
DENSITY MATRIX
HIGH SPIN STATES
IRON
LIGANDS
RENORMALIZATION
SPECTRA
WAVE FUNCTIONS