Characterization of halogen-bridged binuclear metal complexes as hybridized two-band materials

Yamamoto, Shoji

doi:10.1103/physrevb.63.125124

Cited by 43 publications

(37 citation statements)

References 54 publications

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“…21,22 Metal binucleation considerably stimulates the electronic activity. 23,24 A diplatinumiodide chain compound, 25 R 4 [Pt 2 (pop) 4 I] [pop = diphosphonate = P 2 O 5 H 2 ; R = (C 2 H 5 ) 2 NH 2 ], exhibits photo-and pressure-induced phase transitions, [26][27][28][29][30] while its analog without any counter ion, 31 Pt 2 (dta) 4 I (dta = dithioacetate = CH 3 CS 2 ), is of metallic conduction at room temperature and undergoes a double …”

Section: Introductionmentioning

confidence: 99%

Ground-State Properties of a Peierls–Hubbard Triangular Prism

Yamamoto¹,

Ohara²,

Ozaki³

2010

J. Phys. Soc. Jpn.

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Motivated by recent chemical attempts at assembling halogen-bridged transition-metal complexes within a nanotube, we model and characterize a platinum-halide triangular prism in terms of a Peierls-Hubbard Hamiltonian. Based on a group-theoretical argument, we reveal a variety of valence arrangements, including heterogeneous or partially metallic charge-density-wave states. Quantum and thermal phase competitions are numerically demonstrated with particular emphasis on novel insulator-to-metal and insulator-to-insulator transitions under doping, the former of which is of the first order, while the latter of which is of the second order.

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Section: Introductionmentioning

confidence: 99%

Ground-State Properties of a Peierls–Hubbard Triangular Prism

Yamamoto¹,

Ohara²,

Ozaki³

2010

J. Phys. Soc. Jpn.

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“…(c) and (g) are more characterized by charge and spin modulation on the X sublattice, respectively, than by any density wave on the M 2 sublattice. The relevance of the X p z orbitals to these states has fully been demonstrated [13]. The existent MMX complexes consist of two families:…”

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“…We always set t MM and K both equal to unity. This Hamiltonian possesses various density-wave solutions [13], which are schematically shown in Fig. 1.…”

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confidence: 99%

“…Potential magnetic phases have also been proposed [13] and a systematic study of broken-symmetry solutions in the twoband scheme has been presented [13,14]. Let us introduce the 5 6 -filled one-dimensional two-band three-orbital extended Peierls-Hubbard Hamiltonian:…”

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“…Within a single-band description assuming the X p z orbitals to be stably filled, there occurs no quantum competition due to V MX between M-CDW and X-CDW. Once we consider the oxidation of the halogen ions and its contribution to the stabilization of X-CDW [13], increasing V MX more advantageously acts on X-CDW than on M-CDW and indeed accelerates the increase and decrease of their energy gaps (Figs. 4(a ′ ) to 4(c ′ )).…”

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Pressure-induced phase transitions of halogen-bridged binuclear metal complexesR4[Pt2(P

Yamamoto

2001

Phys. Rev. B

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Quasi-one-dimensional halogen (X)-bridged metal (M ) complexes [1], which are referred to as MX chains, have been attracting much interest for several decades. They present an interesting stage performed by electronelectron correlation, electron-lattice interaction, low dimensionality, and d-p orbital hybridization [2]. The Mott and Peierls insulators compete with each other in their ground states, while topological defects such as solitons and polarons appear in their excited states exhibiting unique transport properties [3]. In recent years, a new class of these materials [4][5][6][7], which is characterized by binuclear metal complexes bridged by halogens and is thus referred to as MMX chains, has stimulating further interest in one-dimensional unit-assembled spin-chargelattice coupling systems. In comparison with MX chains,

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Rationalization of the behavior of M₂(CH₃CS₂)₄I (M = Ni, Pt) chains at room temperature from periodic density functional theory and ab initio cluster calculations

et al. 2012

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The electrical conductivities and plausible charge-ordering states in the room temperature (r.t.) phase for MMX chains [Ni(2)(dta)(4)I](∞) and [Pt(2)(dta)(4)I](∞) (dta = CH(3)CS(2)(-)) have been analyzed with periodic density functional theory (DFT) and correlated ab initio calculations combined with the effective Hamiltonian theory. Periodic DFT calculations show a more delocalized nature of the ground state in [Pt(2)(dta)(4)I](∞) compared to [Ni(2)(dta)(4)I](∞), which features a rather large energy gap between the occupied and empty bands, and charge polarized dimer units. A larger electrical conductivity for the Pt chain can be expected, especially because the Fermi level lies within a band with contributions from Pt and I orbitals. Electronic structure parameters extracted from ab initio cluster calculations show that the large difference between the observed conductivities at 300 K for Ni and Pt compounds, of 3 orders of magnitude, cannot be explained from the parameters extracted from an embedded M(2)(dta)(4)I(2) dimer fragment alone. When tetramer fragments are considered, we observe that the interdimer transfer integral (t) between neighboring M(2) units connected by an iodine atom at correlated level is comparable in both chains. On the other hand, the energy to transfer an electron from a dimer to the neighboring one (Coulomb repulsion U) is three times larger in the Ni compound with respect to the Pt chain, in line with the poor conductivity of the former. The electronic structure of the M(4)(dta)(8)I(3) fragment points to an alternate charge-polarization state for Ni and an average valence state for Pt when the r.t. X-ray structure is considered.

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Characterization of halogen-bridged binuclear metal complexes as hybridized two-band materials

Cited by 43 publications

References 54 publications

Ground-State Properties of a Peierls–Hubbard Triangular Prism

Ground-State Properties of a Peierls–Hubbard Triangular Prism

Pressure-induced phase transitions of halogen-bridged binuclear metal complexesR4[Pt2(P

Rationalization of the behavior of M₂(CH₃CS₂)₄I (M = Ni, Pt) chains at room temperature from periodic density functional theory and ab initio cluster calculations

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Characterization of halogen-bridged binuclear metal complexes as hybridized two-band materials

Cited by 43 publications

References 54 publications

Ground-State Properties of a Peierls–Hubbard Triangular Prism

Ground-State Properties of a Peierls–Hubbard Triangular Prism

Pressure-induced phase transitions of halogen-bridged binuclear metal complexesR4[Pt2(P

Rationalization of the behavior of M2(CH3CS2)4I (M = Ni, Pt) chains at room temperature from periodic density functional theory and ab initio cluster calculations

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Rationalization of the behavior of M₂(CH₃CS₂)₄I (M = Ni, Pt) chains at room temperature from periodic density functional theory and ab initio cluster calculations