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Two-level quantum systems are fundamental physical models that continue to attract growing interest due to their crucial role as a building block of quantum technologies. The exact analytical solution of the dynamics of these systems is central to control theory and its applications, such as that to quantum computing. In this study, we reconsider the two-state charge transfer problem by extending and using a methodology developed to study (pseudo)spin systems in quantum electrodynamics contexts. This approach allows us to build a time evolution operator for the charge transfer system and to show new opportunities for the coherent control of the system dynamics, with a particular emphasis on the critical dynamic region around the transition state coordinate, where the avoided crossing of the energy levels occurs. We identify and propose possible experimental implementations of a class of rotations of the charge donor (or acceptor) that endow the electronic coupling matrix element with a time-dependent phase that can be employed to realize controllable coherent dynamics of the system across the avoided level crossing. The analogy of these rotations to reference frame rotations in generalized semiclassical Rabi models is discussed. We also show that the physical rotations in the charge-transfer systems can be performed so as to implement quantum gates relevant to quantum computing. From an exquisitely physical–mathematical viewpoint, our approach brings to light situations in which the time-dependent state of the system can be obtained without resorting to the special functions appearing in the Landau–Zener approach. [ABSTRACT FROM AUTHOR]

Two-level quantum systems are building blocks of quantum technologies, where the qubit is the basic unit of quantum information. The ability to design driving fields that produce prespecified evolutions of relevant physical observables is crucial to the development of such technologies. Using vector algebra and recently developed strategies for generating solvable two-level Hamiltonians, we construct the general solution to the inverse problem for a spin in a time-dependent magnetic field and its extension to any two-level system associated with fictitious spin and field. We provide a general expression for the field that drives the dynamics of the system so as to realize prescribed time evolutions of the expectation values of the Pauli operators and the autocorrelation of the Pauli vector. The analysis is applied to two-state charge transfer systems, showing that the charge transfer process can be seen as a motion of the state of the associated fictitious qubit on the Bloch sphere, and that the expectation values of the related Pauli operators describe the interference between the two differently localized electronic states and their population difference. Our formulation is proposed as a basic step towards potential uses of charge transfer in quantum computing and quantum information transfer. [ABSTRACT FROM AUTHOR]

The influence of carotenoid triplet states on the Qy electronic transitions of chlorophylls has been observed in experiments on light-harvesting complexes over the past three decades, but the interpretation of the resulting spectral feature in the triplet minus singlet (T–S) absorption spectra of photosystems is still debated, as the physical–chemical explanation of this feature has been elusive. Here, we resolve this debate, by explaining the T–S spectra of pigment complexes over the Qy-band spectral region through a comparative study of chlorophyll–carotenoid model dyads and larger pigment complexes from the main light harvesting complex of higher plants (LHCII). This goal is achieved by combining state-of-the-art time-dependent density functional theory with analysis of the relationship between electronic properties and nuclear structure, and by comparison to the experiment. We find that the special signature in the T–S spectra of both model and natural photosystems is determined by singlet-like triplet excitations that can be described as effective singlet excitations on chlorophylls influenced by a stable electronic triplet on the carotenoid. The comparison with earlier experiments on different light-harvesting complexes confirms our theoretical interpretation of the T–S spectra in the Qy spectral region. Our results indicate an important role for the chlorophyll–carotenoid electronic coupling, which is also responsible for the fast triplet–triplet energy transfer, suggesting a fast trapping of the triplet into the relaxed carotenoid structure. The gained understanding of the interplay between the electronic and nuclear structures is potentially informative for future studies of the mechanism of photoprotection by carotenoids. [ABSTRACT FROM AUTHOR]

We report the step-by-step construction of the exact, closed and explicit expression for the evolution operator U (t) of a localized and isolated qubit in an arbitrary time-dependent field, which for concreteness we assume to be a magnetic field. Our approach is based on the existence of two independent dynamical invariants that enter the expression of S U (2) by means of two strictly related time-dependent, real or complex, parameters. The usefulness of our approach is demonstrated by exactly solving the quantum dynamics of a qubit subject to a controllable time-dependent field that can be realized in the laboratory. We further discuss possible applications to any S U (2) model, as well as the applicability of our method to realistic physical scenarios with different symmetry properties. [ABSTRACT FROM AUTHOR]

The effects of intervening water molecules on the electron self-exchange of azurin (Az) are studied by using a newly developed ab-initio method to calculate transfer integrals between molecular sites. The results have shown that this effect is attributed to the simultaneous action of two competing effects like the electrostatic interaction of water with the protein subsystem and its ability to mediate electron-transfer (ET) coupling pathways.

In this work I develop and apply a theoretical method for calculating effective electronic couplings (or transfer integrals) between redox sites involved in hole or electron transfer reactions. The resulting methodology is a refinement and a generalization of a recently developed approach for transfer integral evaluation. In fact, it holds for any overlap between the charge-localized states used to represent charge transfer (CT) processes in the two-state model. The presented theoretical and computational analyses show that the prototype approach is recovered for sufficiently small overlaps. The method does not involve any empirical parameter. It allows a complete multielectron description, therefore including electronic relaxation effects. Furthermore, its theoretical formulation holds at any value of the given reaction coordinate and yields a formula for the evaluation of the vertical excitation energy (i.e., the energy difference between the adiabatic ground and first-excited electronic states) that rests on the same physical quantities used in transfer integral calculation. In this paper the theoretical approach is applied to CT in B-DNA base dimers within the framework of Density Functional Theory (DFT), although it can be implemented in other computational schemes. The results of this work, as compared with previous Hartree–Fock (HF) and post-HF evaluations, support the applicability of the current implementation of the method to larger π-stacked arrays, where post-HF approaches are computationally unfeasible. [ABSTRACT FROM AUTHOR]

The effects of intervening water molecules on the electron self-exchange reaction of azurin (Az) are analyzed by performing a conformational sampling on the water medium. The results are discussed in terms of the interplay between different electron-transfer (ET) pathways controlled by the conformational changes of one of the water molecules through its electrostatic influence.