Jahn-Teller effect in liquids: General principles and a molecular-dynamics simulation of the cupric ion in water

Curtiss, Larry A.; Halleý, J. W.; Wang, X. R.

doi:10.1103/physrevlett.69.2435

Cited by 27 publications

(21 citation statements)

References 10 publications

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“…The pattern of a set of water molecules defining a plane bearing the metal cation is the common and persistent motif of the set of structures compatible with the highly dynamic behavior of the system. Therefore, the main conclusion of this work is that Jahn-Teller in solution must be better understood as a dynamical effect as earlier proposed by Curtiss et al, 59 based on classical MD, and later by Blumberger et al…”

Section: Figsupporting

confidence: 59%

“…The high fluxionality of this system invoked by several authors from theoretical examination of the dynamics of the system 12,14,59 provides a rationalization of the results obtained, according to which six-, five-, and four-coordinated structures would coexist dynamically in solution.…”

Section: Discussionmentioning

confidence: 71%

“…Frank et al have recently pointed out how for the preferred Cu͑II͒ aquaion arrangement should not be cached in the crystal structure geometries alone. 18 As proposed by Curtiss et al 59 JT effect should be understood as a kind of dynamical symmetry breaking which is only appearing on short time scales, being washed out at longer time scales. We believe that the spectroscopical peculiarities associated to the double channel appearing in the ionization pro- cess of the Cu͑II͒ hydrate in water provide a fairly good background to further XAS molecular-dynamics combined studies.…”

Section: Figmentioning

confidence: 98%

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The hydration of Cu2+: Can the Jahn-Teller effect be detected in liquid solution?

Chaboy

Muñoz‐Páez

Merkling

et al. 2006

The Journal of Chemical Physics

114

125

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The long elusive structure of Cu͑II͒ hydrate in aqueous solutions, classically described as a Jahn-Teller distorted octahedron and recently proposed to be a fivefold coordination structure ͓Pasquarello et al., Science 291, 856 ͑2001͔͒, has been probed with x-ray-absorption spectroscopy by performing a combined theoretical and experimental analysis. Two absorption channels were needed to obtain a proper reproduction of the x-ray-absorption near-edge structure ͑XANES͒ region spectrum, as already observed in other Cu͑II͒ complexes ͓Chaboy et al., Phys. Rev. B 71, 134208 ͑2005͔͒. The extended x-ray-absorption fine-structure ͑EXAFS͒ spectrum was analyzed as well within this approach. Quite good reproductions of both XANES and EXAFS spectra were attained for several distorted and undistorted structures previously proposed. Nevertheless, there is not a clearly preferred structure among those including four-, five-, and sixfold coordinated Cu͑II͒ ions. Taking into account our results, as well as many more from several other authors using different techniques, the picture of a distorted octahedron for the Cu͑II͒ hexahydrate in aqueous solution, paradigm of the Jahn-Teller effect, is no longer supported. In solution a dynamical view where the different structures exchange among themselves is the picture that better suits the results presented here.

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Section: Figsupporting

confidence: 59%

Section: Discussionmentioning

confidence: 71%

Section: Figmentioning

confidence: 98%

See 1 more Smart Citation

The hydration of Cu2+: Can the Jahn-Teller effect be detected in liquid solution?

Chaboy

Muñoz‐Páez

Merkling

et al. 2006

The Journal of Chemical Physics

114

125

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“…However, in these simulations atoms are modeled as charges. One possible explanation of how the simulations could capture the local distortion is that the parameters of the potentials used for description of short‐range order between Cu 2+ –O 2− can mimic the Jahn‐Teller effect in addition to smaller size of Cu 2+ cation.…”

Section: Resultsmentioning

confidence: 99%

Critical role of cationic local stresses on the stabilization of entropy‐stabilized transition metal oxides

2020

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Entropy‐stabilized transition metal oxides ([MgNiCoCuZn]O) (ESO) in recent years have received considerable attention owing to their unique functional properties. Solution combustion and solid state syntheses resulted in crystallites varying from 5‐15 nm to 3‐5 μm respectively. Phase stability studies showed that all the systems containing Cu2+ ions in the ESO lattice segregated upon slow cooling in the furnace. It was only when ESO was quenched in air from 1000°C the lattice stabilized to a single phase. Experiments concomitant with molecular dynamics (MD) simulations demonstrated that the local stress fields around the cations played a critical role in stabilizing the single phase. The local stress fields are a result of Jahn‐Teller distortion induced by the Cu2+ ions in the lattice. It is clearly established that in the absence of the minimization of the local stress fields around the Cu2+ ions, segregation leading to the formation of a multi‐phase material is imminent for this particular composition.

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“…Note that Almedia et al [31] shed light on the transformation of coordination numbers. In short, theoretical calculations [23] [20]. This fact implies that further investigations will be valuable and informative.…”

Section: Introductionmentioning

confidence: 98%

Fragment molecular orbital−based molecular dynamics (FMO-MD) simulations on hydrated Cu(II) ion

Kato

Fujiwara

Komeiji

et al. 2014

CBIJ

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A simulation protocol based on fragment molecular orbital−based molecular dynamics (FMO-MD) was applied to a droplet model consisting of a divalent copper ion and 64 water molecules. The total energy and forces were evaluated at the unrestricted Hartree-Fock (UHF) level with three-body fragment correction (FMO3). Two MD runs were performed: one with a six-coordination setting and the other with a five-coordination setting in the first hydration shell. Both runs resulted in the main peak position of the Cu-O radial distribution function at 2.02 Å, in reasonable agreement with the experimental data. The O-Cu-O angular distribution function showed different characteristics between the two cases.

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Jahn-Teller effect in liquids: General principles and a molecular-dynamics simulation of the cupric ion in water

Cited by 27 publications

References 10 publications

The hydration of Cu2+: Can the Jahn-Teller effect be detected in liquid solution?

The hydration of Cu2+: Can the Jahn-Teller effect be detected in liquid solution?

Critical role of cationic local stresses on the stabilization of entropy‐stabilized transition metal oxides

Fragment molecular orbital−based molecular dynamics (FMO-MD) simulations on hydrated Cu(II) ion

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