Electric Field Control of Spin-Dependent Dissipative Electron Transfer Dynamics in Mixed-Valence Molecules

Palii, Andrew; Clemente‐Juan, Juan M.; Coronado, Eugenio; Tsukerblat, Boris

doi:10.1021/jp512102n

Cited by 10 publications

(8 citation statements)

References 67 publications

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“…Among the different classes of electrically switchable systems, mixed-valence (MV) magnetic metal clusters − are especially attractive and promising because of the presence of mobile electrons or holes in their structures. Such mobile charges can be polarized by the electric field and, moreover, in many specific cases field-induced polarization proves to be spin-dependent because of the strong correlation between the charge and spin degrees of freedom.…”

Section: Introductionmentioning

confidence: 99%

Electric Field Control of Spin States in Trigonal Two-Electron Quantum Dot Arrays and Mixed-Valence Molecules: I. Electronic Problem

et al. 2018

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In the context of our studies of the electric field control over stimuli-responsive molecular materials, in this article, we report a detailed theoretical analysis of the electric field control of the spin states, magnetic properties, and charge distributions in the trigonal trimeric systems comprising a pair of mobile electrons or holes. Such systems are exemplified by “physical” molecules composed of semiconductor quantum dots accommodating unpaired electrons as well as by proper chemical systems representing trigonal trimeric mixed-valence clusters in which the two mobile electrons are delocalized over three spinless cores. In part I of the paper, we consider the electronic interactions (inter- and intrasite Coulomb repulsion, electron transfer, and Stark interaction) in quantum dot arrays and mixed-valence molecules, whereas part II deals with the vibronic approach in which the interaction between the mobile electrons and the molecular vibrations is taken into account as well. A complicated interplay between the electron transfer and the localizing effect of the field is shown to result in a series of interesting magnetic effects. We demonstrate this by changing the magnitude of the electric field and/or its orientation with respect to the axes of the system, one can reach an efficient electric field control over the magnetic and electric properties of the considered systems. Particularly, under some conditions (described in the paper), the electric field of attainable strength is shown to induce spin switching from the ground state possessing the spin S = 1 to that with S = 0. Such a possibility to control the spin states of single molecules and analogous systems using an external electric field is of current interest for molecular spintronics.

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Section: Introductionmentioning

confidence: 99%

Electric Field Control of Spin States in Trigonal Two-Electron Quantum Dot Arrays and Mixed-Valence Molecules: I. Electronic Problem

et al. 2018

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“…The recognition of MV compounds as a potential mining source for DNP polarizing agents opens many possibilities for the tuning of the ET properties of these polarizing agents via structural modifications. For example, drawing on the vast amount of literature on MV compounds, it is well-known that one can tune the electron transfer integral by modifying the bridge length between the two redox moieties. , Besides structural modifications, environment-induced electronic rearrangements can play a similar role, for example, excitation, coordination, solvation, external pressure, and external electric or magnetic fields have all been either actually attempted or proposed. ,, It is for this reason that MV compounds have been termed a “playground for electrons and holes” …”

Section: Discussionmentioning

confidence: 99%

“…2, 25 Besides structural modifications, environment-induced electronic rearrangements can play a similar role, for example, excitation, coordination, solvation, external pressure, and external electric or magnetic fields have all been either actually attempted or proposed. 49,58,59 It is for this reason that MV compounds have been termed a "playground for electrons and holes".…”

Section: ■ Conclusionmentioning

confidence: 99%

Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids

et al. 2021

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Recent experiments have shown that the organic free radical 1,3bisdiphenylene-2-phenylallyl (BDPA) can induce an Overhauser effect dynamic nuclear polarization in insulating solids, a feat previously considered not to be possible. Here, we establish that this peculiar ability of the BDPA radical stems from its mixed-valence nature and the ensuing intramolecular charge transfer. Using state-of-the-art DMRGSCF calculations, we confirm the class II mixed-valence nature of BDPA with the characteristic double-well potential energy surface, and we investigate the mechanism of the consequent electron hopping. A twocomponent vibronic Hamiltonian is then employed to compute the rate of electron hopping from a quantum dynamical time-propagation of the density matrix. The predicted hyperfine coupling oscillations indeed fall within the frequency range required for an Overhauser effect. The paradigm of mixed-valence compounds as a mining source opens many possibilities for the development and fine tuning of novel polarizing agents.

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“…Such magnetic MV clusters are of current interest in molecular electronics and spintronics. − Also, one can expect that similar “physical molecules” exhibiting double exchange can be composed of magnetic quantum dots − comprising different numbers of unpaired electrons. In this regard, it is worthwhile revealing the possibility of using clusters comprising paramagnetic cores as tetrameric square-planar cells and thus considerably extending the class of systems suitable as QCA cells.…”

Section: Introductionmentioning

confidence: 99%

Mixed-Valence Magnetic Molecular Cell for Quantum Cellular Automata: Prospects of Designing Multifunctional Devices through Exploration of Double Exchange

et al. 2020

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In this article, we propose to use multielectron square-planar mixedvalence (MV) molecules as molecular cells for quantum cellular automata (QCA) devices. As distinguished from previous proposals in this area, in multielectron cells, the electronic pair encoding binary information is shared among localized spins ("spin cores"). Hopefully, this will allow exploring not only charge degrees of freedom encoding binary information in the antipodal electronic distributions but also spin degrees of freedom through the magnetic interactions such as double exchange and Heisenberg−Dirac−Van Vleck (HDVV) exchange. To develop the proposed route, the square-planar tetrameric cells for QCA have been theoretically modeled. The considered cells comprise a pair of excess electrons shared among four spin cores and hence they exhibit double exchange and HDVV exchange. Such cells can be based either on the square-planar mixed-valence molecular clusters or on the similar square arrays of multielectron quantum dots. The detailed case study of the cell representing the transition-metal tetramer of the type of d 2 −d 2 −d 1 −d 1 shows that depending on the relative strength of the second-order double exchange and HDVV exchange, the isolated cell has either ground localized spin-triplet or one of the two delocalized spin-singlets, exhibiting different extents of electron delocalization. Due to different sensitivities of these states to the quadrupole electrostatic field induced by the polarized neighboring driver cell, the latter is shown to be able to produce switching between different ground states (including spin-switching between spin-singlet and spin-triplet), which leads to the nonmonotonic behavior of the cell−cell response function. This opens new perspectives for the designing of multifunctional devices combining the QCA functionality with spin-switching function.

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Electric Field Control of Spin-Dependent Dissipative Electron Transfer Dynamics in Mixed-Valence Molecules

Cited by 10 publications

References 67 publications

Electric Field Control of Spin States in Trigonal Two-Electron Quantum Dot Arrays and Mixed-Valence Molecules: I. Electronic Problem

Electric Field Control of Spin States in Trigonal Two-Electron Quantum Dot Arrays and Mixed-Valence Molecules: I. Electronic Problem

Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids

Mixed-Valence Magnetic Molecular Cell for Quantum Cellular Automata: Prospects of Designing Multifunctional Devices through Exploration of Double Exchange

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