Vibronic coupling effects in trimeric mixed-valence clusters

The spectrum of a trimeric mired-valence cluster d₁–d₁–d₂ is calculated in the Piepha-Krausz-Schatz vibronic model. Based on the vibronic spectra obtained magnetic properties of the d₁–d₁–d₂ cluster are investigated It is shown that spin of the system's ground state may change not only as a result of double exchange reduction by vibronic coupling, but also due to a diflerence in the eneqy dependence of the lowest vibronic states on the vibronic coupling constant for diflerent total spin values. Unlike previous studies of vibronic interactions in the d₁–d₁–d₂ cluster, in this study the diagonalizations of the vibronic-coupling and double-exchange matrices are fuljilled simultaneously, using Lanczos' method. Due to this, all types 4 vibronic state mixing by double exchange could be taken into account properly.Moldova State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 20–32, September–October, 1993.Translated by L. Smolina     

Vibronic reduction of Heisenberg and double exchange in multielectron mixed-valency clusters

Vibronic reduction is considered for Coulomb interaction between centers for Heisenberg and double exchange in multielectron mixed-valency d²-d³ clusters. A simplified multimode vibration model indicates how effects arise via vibrations from the correlation interaction between electron shells. Vibronic reduction in double exchange can alter the magnetic parameters for the cluster's ground state.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 114–121, March–April, 1992.     

Determination of exchange interaction parameters in heterospin exchange clusters

An approach to calculation of the intracluster exchange parameters of molecular heterospin systems is proposed. This approach allows one to estimate the model errors of the parameters to be determined. The efficiency of this technique is demonstrated by analyzing the experimental data for the Cu(II), Ni(II), and Co(II) molecular complexes with stable nitroxides.     

Vibronic interaction in one-dimensional polymer

Asymptotic properties of the “attractive” vibronic coupling in a one-dimensional polymer are analyzed. The strength of the vibronic coupling grows linearly with the size of polymer, which may relate to the softening mechanism of Coulombic repulsive interaction between a Cooper pair of superconducting electrons.     

Vibronic interaction in metalloporphyrin pi-anion radicals

The vibronic (vibrational-electronic) interactions in the pi-anion radicals of the metalloporphyrins (M=Cr, Mn, Fe, Co, Ni, Cu, and Zn), which show delocalized D4h structures in the neutral states, are discussed using B3LYP density-functional-theory calculations. The B1g and B2g modes of vibration can remove the degenerate 2Eg state of the pi-anion radicals in the D4h symmetric structures to lead to rectangular and diamond D2h distortions, respectively. Calculated vibronic coupling constants demonstrate that the B1g modes of vibration better couple with the degenerate electronic state, leading to the rectangular D2h distortion. In particular, the B1g modes of nu10 and nu11, which have dominant contributions from Calpha-Cm and Cbeta-Cbeta stretching, give large vibronic coupling constants in the pi-anion radicals. The vibronic coupling constant can be viewed as the Jahn-Teller distortion force, and therefore these C-C stretching B1g modes will play a central role in the Jahn-Teller effect of the pi-anion radicals of the metalloporphyrins.     

Vibronic effects in elastic scattering of electrons

A method for obtaining general equations for the scattered intensities from vibronic systems is given. The approximate formulas obtained are used to calculate the effects on the electron diffraction pattern for molecules with doubly degenerate electronic E terms interacting with e-type vibrations (Ee-type of problem). The results of the approximate calculations are compared to more precise results, based on numerical solution of the vibronic problem.     

Vibronic effects in porphyrin optical-absorption band splitting

A four-orbital model is applied to the joint effects from an external field, sym-metry b_1g, and vibronic interaction showing displacement with the same symmetry on the forms of the adiabatic potentials for the B and Q metal-porphyrin states. The high-symmetry nuclear configurtion in state Q is distorted more than that in state B, which explains the substantially larger splitting for the Q band by comparison with B in the presence of low-symmetry substituents and/or external fields, as well as why the splitting is dependent on the metal.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 23, No. 6, pp. 699–705, November–December, 1987.I am indebted to B. G. Vekhter for fruitful discussions.     

Vibronic interaction and triplet state photophysics of phenylisatin and oxindole

Photophysical study of phenylisatin and oxindole triplet states have been made at room temperature and in different glasses at 77K. Qualitatively, in all respects the compounds have identical spectroscopic characteristics. Phosphorescence emission, excitation along with their polarization and lifetime suggest that a perturbation of the zero-point level of emitting state (³ππ*) by a close-lying triplet state (³nπ*) leads to a number of new spectral features. The experimental observations have been interpreted satisfactorily in terms of a switch (³ππ* state to ³nπ*) in the character of the lowest triplet states (T₁ and T₂) and also a similar switch in the character of the excited singlet states S₁ and S₂ for a change of glass matrix from MCH to ethanol. Invoking of first order and second order spin-orbit coupling explains the phosphorescence emission unambiguously.     

Vibronic dressed electronic states and nonadiabatic effects in polyacetylene

Conditions for low and high T_c superconductors following from the nonadiabatic electron-vibrational theory at ab initio level have been obtained. According to the presented results, the supercurrent is realized by the motion of the ground-state electronic-charge distribution of the fully occupied band. The motion of the electronic-charge distribution is conditioned by the newly arisen, nondissipative degrees of freedom of nuclear, Jahn–Teller-like, microflows. The Meissner effect is also interpreted.     

Vibronic theory of substitution effects in molecules and complexes

Mutual influence of ligands and isomer relative stabilities in molecules and complexes ML_n–kXY ... Z are considered using the perturbation approach. Symmetry aspects of these phenomena are emphasized.     

Double exchange in polynuclear mixed-valence clusters

A method for calculating the energies of the tunnel states of mixed-valence, clusters is proposed. It is based on the secondary quantization technique and allows one to obtain analytical expressions for all matrix elements that appear in double exchange theory as well as to determine the microstructures of the parameters of this theory. The energy spectra of trimeric systems are calculated with allowance made for the three-center transfer integrals, and the magnetic properties of these systems are investigated. Moldova State University. Translated fromZhurnal Struktumoi Khimii, Vol. 36, No. 4, pp. 644–653, July–August, 1995. Translated by I. Izvekova     

Pyrazine-2,3-dicarboxylate-bridged polymeric and dinuclear complexes involving decameric water clusters

Two copper(II) complexes of pyrazine-2,3-dicarboxylate (H₂pzdc) with 2-aminopyridine (apy), {(Hapy)₂[Cu(μ-pzdc)₂]} _n (1) and 1,10-phenanthroline (phen), [Cu₂(μ-pzdc)(phen)₄][N(CN)₂]₂?·9H₂O (2) have been synthesized and structurally characterized. Complex 1 consists of a pyrazine-2,3-dicarboxylate bridging across a double chain, while 2 exists as a dinuclear complex in which two Cu(II) ions are bridged by pzdc via different coordination modes. One Cu(II) ion in the binuclear complex is a distorted octahedron, while the other Cu(II) is a distorted trigonal bipyramid. A chair-like decameric water cluster composed of two pentamers and a shared-edge tetramer is detected, which further associate into a 1-D tape with dicyanamide anions by hydrogen bonds.     

Structural and electronic effects on the exchange interactions in dinuclear bis(phenoxo)-bridged copper(II) complexes

Computational methods based on density functional theory have been employed to analyze the magnetic properties of dinuclear bis(phenoxo)-bridged Cu^II complexes. While the largest part of complexes in that family show antiferromagnetic coupling, we focus our study on those cases with distorted geometries that present ferromagnetic behaviour. The calculations reproduce such a magnetic behaviour, and a structural analysis reveals the main role played by several structural parameters, such as the Cu–O–Cu bridging angle. The out-of-plane shift of the phenoxo ring and the hinge distortion of the Cu₂O₂ central framework that are also important for similar hydroxo and alkoxo complexes. In this case the conformation of the phenoxo groups and the rotation of the phenyl rings can also play an important role. The last part of this work is dedicated to analyze the influence of the substituents of the phenoxo ring on the magnetic properties, which is especially important for structures with large out-of-plane shifted phenoxo rings. The presence of π electron releasing groups favours a ferromagnetic coupling.     

Structure and magnetism in Fe-Gd based dinuclear and chain systems. The interplay of weak exchange coupling and zero field splitting effects

The synthesis and characterization of two Fe-Gd systems based on bpca(-) (Hbpca = bis(2-pyridilcarbonyl)amine) as bridging ligand is presented, taking the systems as a case study for structure-property correlations. Compound 1, [Fe(LS)(II)(μ-bpca)(2)Gd(NO(3))(2)(H(2)O)]NO(3)·2CH(3)NO(2), is a zigzag polymer, incorporating the diamagnetic low spin Fe(LS)(II) ion. The magnetism of 1 is entirely determined by the weak zero field splitting (ZFS) effect on the Gd(III) ion. Compound 2 is a Fe(III)-Gd(III) dinuclear compound, [Fe(LS)(III)(bpca)(μ-bpca)Gd(NO(3))(4)]·4CH(3)NO(2)·CH(3)OH, its magnetism being interpreted as due to the antiferromagnetic coupling between the S(Fe) = ? and S(Gd) = 7/2 spins, interplayed with the local ZFS on the lanthanide center. In both systems, the d-f assembly is determined by the bridging capabilities of the ambidentate bpca(-) ligand, which binds the d ion by a tridentate moiety with nitrogen donors and the f center by the diketonate side. We propose a spin delocalization and polarization mechanism that rationalizes the factors leading to the antiferromagnetic d-f coupling. Although conceived for compound 2, the scheme can be proposed as a general mechanism. The rationalization of the weak ZFS effects on Gd(III) by multiconfiguration and spin-orbit ab initio calculations allowed us to determine the details of the small but still significant anisotropy of Gd(III) ion in the coordination sites of compounds 1 and 2. The outlined methodologies and generalized conclusions shed new light on the field of gadolinium coordination magnetochemistry.     

Isotopic exchange reactions between iron-sulphur-nitrosyl clusters and nitrite

The anion [Fe₄S₃(NO)₇]⁻ undergoes slow exchange with labelled nitrite [¹⁵NO₂]⁻ to yield a product [Fe₄S₃(¹⁴NO)(¹⁵NO)₆]⁻ in which complete isotopic exchange has occurred at the basal Fe(NO)₂ groups, but with no exchange at the apical Fe(NO) group. The neutral Fe₄S₄(NO)₄ reacts rapidly with [¹⁵NO₂⁻ to give fully exchanged [Fe₄S₃(¹⁵NO)₇]⁻, and it is proposed that the conversion proceeds by fragmentation, followed by complete isotopic exchange and rapid reassembly. The binuclear anion [Fe₂S₂(NO)₄]²⁻ also yields, with [¹⁵NO₂]²⁻ in CD₂Cl₂ solution, the fully exchanged [Fe₄S₃(¹⁵NO)₇]⁻, and a mechanism involving successive fragmentation, exchange and reassembly steps is proposed; however in aqueous solution, a clean exchange reaction occurs to give [Fe₂S₂(¹⁵NO)₄]²⁻. Neutral binuclear esters Fe₂(SR)₂(NO)₄ (R = Me, Et, or Ph) with [¹⁴NO₂]⁻ yield the mononuclear paramagnetic [Fe(¹⁴NO)₂(¹⁴NO₂)₂]⁻, and with [¹⁵NO₂]⁻ the analogous [Fe(¹⁵NO)₂(₁₅NO₂)₂]⁻.     

Vibronic coupling to T1 and T2 vibrations and the Jahn-Teller effect in transition-metal exchange tetraclusters

A study has been made on the four-center Jahn-Teller effect in tetrahedral transition-metal tetraclusters of M₄X₄L₄ and M₄OX₆L₄ types (M metal, X and L ligands) for twofold orbital degeneracy at each of the four centers and strong coupling between the electronic states there and the cluster vibrations. An analytic expression is derived for the adiabatic potential in the space of all active vibrations. The features of the adiabatic-potential sheets in the T₁ and T₂ vibration space are examined, and the spectrum is derived for the lowest vibronic states. There is a qualitative discussion of the system dynamics.Translated from Teoreti-cheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 6, pp. 657–665, November–December, 1987.     

Transmission of trans effects in dinuclear complexes.

The substitution of a terminal hydride ligand in the complexes [Ir(2)(mu-H)(mu-Pz)(2)H(3)(L)P(i)Pr(3))(2)] (L = NCCH(3) (1) or pyrazole (3)) by chloride provokes a significant change in the lability of the L ligand, despite the fact that the substituted hydride and the L ligand lie in opposite extremes of the diiridium(III) complexes. Detailed structural studies of complex 3 and its chloro-trihydride analogue [Ir(2)(mu-H)(mu-Pz)(2)H(2)Cl(HPz)(P(i)Pr(3))(2)] (4) have shown that this behavior is a consequence of the transmission of ligand trans effects from one extreme of the molecule to the other, with the participation of the bridging hydride. Extended Hückel calculations on model diiridium complexes have suggested that such trans effect transmissions are due to the formation of molecular orbitals of sigma symmetry extended along the backbones of the complexes. This is also an expected feature for metal-metal bonded complexes. The feasibility of the transmission of ligand trans effects and trans influences through metal-metal bonds and its relevance to the understanding of both the reactivity and structures of metal-metal bonded dinuclear compounds have been substantiated through structural studies and selected reactions of the diiridium(II) complexes [Ir(2)(mu-1,8-(NH)(2)naphth)I(CH(3))(CO)(2)(P(i)Pr(3))(2)] (isomers 6 and 7) and their cationic derivatives [Ir(2)(mu-1,8-(NH)(2)naphth)(CH(3))(CO)(2)(P(i)Pr(3))(2)](CF(3)SO(3)) (isomers 8 and 9).