Spin-phonon interactions are known to drive magnetic relaxation in solid-state systems but are generally overlooked as a contribution to spin decoherence through dephasing. Here, we extend quantum master equations to account for coherence terms and describe the full effect of up to two-phonon processes on spin dynamics. We implement this method fully ab initio for a molecule with large magnetization blocking temperature and show that, although strong axial magnetic anisotropy ensures slow magnetic relaxation approaching seconds at 77 kelvins, the superposition of Kramers doublets is coherent for less than 10 nanoseconds due to a two-phonon pure dephasing mechanism. This process, in principle, applies to any quantum system interacting with a thermal bath of phonons, advancing our understanding of quantum decoherence in solid-state systems.
Spin-phonon interactions are known to drive magnetic relaxation in solid-state systems but are generally overlooked as a contribution to spin decoherence through dephasing. Here, we extend quantum master equations to account for coherence terms and describe the full effect of up to two-phonon processes on spin dynamics. We implement this method fully ab initio for a molecule with large magnetization blocking temperature and show that, although strong axial magnetic anisotropy ensures slow magnetic relaxation approaching seconds at 77 kelvins, the superposition of Kramers doublets is coherent for less than 10 nanoseconds due to a two-phonon pure dephasing mechanism. This process, in principle, applies to any quantum system interacting with a thermal bath of phonons, advancing our understanding of quantum decoherence in solid-state systems.
Molecular spins are promising candidates for quantum information science, leveraging coherent electronic spin states for quantum sensing and computation. However, the practical application of these systems is hindered by electronic spin decoherence, driven by interactions with nuclear spins in the molecule and the surrounding environment at low temperatures. Predicting dephasing dynamics remains a formidable challenge due to the complexity of the spin bath. In this work, we develop a non-Markovian time-convolutionless master equation to treat an electronic spin coupled to a nuclear-spin bath. By relating ab initio electronic structure parameters directly to the decoherence dynamics, we provide a framework that accounts for pure dephasing in the low-temperature limit. We apply this method to a series of molecular qubit candidates and demonstrate good agreement with experimental relaxation trends. This approach offers a computationally efficient path for the prediction of low-temperature decoherence trends in molecular spin systems.
Single molecule magnets are novel mesoscopic materials exhibiting both classical and quantum properties. Revealing the decoherence and entanglement mechanisms in these systems is crucial for the applications in quantum information technologies. In this thesis, quantum tunneling of magnetization is studied in single molecule magnet dimer [Mn4]2. Motivated by the recent experiments demanding the modification of the current theories, phonon mediated spin bath decoherence model is proposed. In the first part of the thesis, the magnetization of the [Mn4]2 dimer under external magnetic field is investigated. Alternative entangled spin states involved in quantum tunnelings are identified by means of the exact solution of the Schrödinger equation and the Landau-Zener-Stückelberg method. Later, a decoherence model is introduced in which the interaction between the single molecule magnet (central spin) and spin bath is mediated by phonons in a coherent state or thermal distribution. It is observed that the decoherence factor decays in a Gaussian fashion and it becomes independent of the phonon frequencies at short times for coherent states and low temperature thermal distribution. In the former case, if the phonon energies are much larger than spin-phonon coupling or bath spins are fully polarized, decoherence time becomes independent of the initial phonon state. For the thermal state case, phonons play more important role in decoherence with increasing temperature. Possible effects of the temperature on spin bath contribution to decoherence is discussed. Then, the effect of entangled environment on decoherence is analyzed. Entanglement within environment is shown to reduce the decoherence of central spin. Also, the entanglement dynamics of the central bipartite spin system is studied. Classification of the Bell states is examined for common spin bath, and separate spin baths. Last part of the thesis is the analysis of dephasing in entangled qutrits (three level quantum systems) under the classical noise, and quantum decoherence. Density matrix formalism is shown to give equivalent results for both cases. For common and separate baths, robust and fragile Bell-like qutrit states were determined, and Horodecki's bound entangled state is shown to be more robust to decoherence in the latter case.
Understanding the effect of vibrations on the relaxation process of individual spins is crucial for implementing nanosystems for quantum information and quantum metrology applications. In this work, we present a theoretical microscopic model to describe the spin-lattice relaxation of individual electronic spins associated to negatively charged nitrogen-vacancy centers in diamond, although our results can be extended to other spin-boson systems. Starting from a general spin-lattice interaction Hamiltonian, we provide a detailed description and solution of the quantum master equation of an electronic spin-one system coupled to a phononic bath in thermal equilibrium. Special attention is given to the dynamics of one-phonon processes below 1 K where our results agree with recent experimental findings and analytically describe the temperature and magnetic-field scaling. At higher temperatures, linear and second-order terms in the interaction Hamiltonian are considered and the temperature scaling is discussed for acoustic and quasilocalized phonons when appropriate. Our results, in addition to confirming a T5 temperature dependence of the longitudinal relaxation rate at higher temperatures, in agreement with experimental observations, provide a theoretical background for modeling the spin-lattice relaxation at a wide range of temperatures where different temperature scalings might be expected.
Molecular magnets are ideal systems to probe the realm that borders quantum and classical physics, as well as to study decoherence phenomena in nanoscale systems. The control of the quantum behavior of these materials and their structural characteristics requires synthesis of new complexes with desirable properties which will allow probing of the fundamental aspects of nanoscale physics and quantum information processing. Of particular interest among the magnetic molecular materials are single-molecule magnets (SMMs) and antiferromagnetic (AFM) molecular wheels in which the spin state of the molecule is known to behave quantum mechanically at low temperatures. In previous experiments the dynamics of the magnetic moment of the molecules is governed by incoherent quantum tunneling. Short decoherence times are mainly due to interactions between molecular magnets within the crystal and interactions of the electronic spin with the nuclear spin of neighboring ions within the molecule. This decoherence problem has imposed a limit to the understanding of the molecular spin dynamics and the sources of decoherence in condensed matter systems. Particularly, intermolecular dipolar interactions within the crystal, which shorten the coherence times in concentrated samples, have stymied progress in this direction. Several recent works have reported a direct measurement of the decoherence time in molecular magnets. This has been done by eliminating the dephasing created by dipolar interactions between neighboring molecules. This has been achieved by a) a dilution of the molecules in a liquid solution to decrease the dipolar interaction by separating the molecules, and b) by polarizing the spin bath by applying a high magnetic field at low temperatures. Unfortunately, both approaches restrict the experimental studies of quantum dynamics. For example, the dilution of molecular magnets in liquid solution causes a dispersion of the molecular spin orientation and anisotropy axes, while the large fields required to polarize the spin bath overcome the anisotropy of the molecular spin. In this thesis I have explored two methods to overcome dipolar interactions in molecular magnets: a) studying the dynamics of molecular magnets in single crystals where the separation between magnetic molecules is obtained by chemical doping or where the high crystalline quality allows observations intrinsic to the quantum mechanical nature of the tunneling of the spin, and b) studying the electronic transport through an individual magnetic molecule which has been carefully placed in a single-electron transistor device. I have used EPR microstrip resonators to measure Fe17Ga molecular wheels within single crystals of Fe18 AFM wheels, as well as demonstrating, for the first time in a Single Molecule Magnet, the complete suppression of a Quantum Tunneling of the Magnetization transition forbidden by molecular symmetry.
Since the development of microsized devices is moving forward at enormous speed, there is huge amount of new industrial opportunities. However such devices also require high precision and understanding of the operating of their constituent parts up to the quantum level. The device of the purely quantum nature being developed so far is quantum computer. However the physical realization of it is still not performed, as the requirements for it are very rigorous. \n \nIn the pioneering work by Loss and DiVincenzo it was suggested to use a spin of electron placed in a quantum dot as an information qubit. Following this work the study of electron or hole spin qubits developed. Both experimental and theoretical tools for studying them greatly advanced. \n \nIn the first part of the thesis we study the phonon-induced decoherence and relaxation of singlet-triplet qubits in the double quantum dots. First of all we consider AlGaAs/GaAs double quantum dots. The important result we present here is the strong dephasing that occurs at large detuning. This dephasing is due to two-phonon process that affects mainly singlet state of the qubit and consequently changes the splitting between singlet and triplet leading to dephasing. Remarkably at small detuning this dephasing process is suppressed and the decoherence time is by orders of magnitude longer than in case of large detuning and is mainly defined by one-phonon process. We also present the dependence of relaxation time and decoherence time on the strength of spin-orbit interaction and different directions of the system. Our results provide a deeper insight into the recently obtained experimental data. \n \nWe also studied Si/SiGe quantum dots as a potential candidate for a qubit. Apart from the absence of hyperfine interaction and bulk spin-orbit interaction in the isotopically purified 28Si, its electron-phonon interaction is different from GaAs that also leads to longer qubit lifetimes. We study S-T− qubit near the anticrossing of the basis states. This particular region is interesting due to possibilities in operating the qubit. We show that the type of singlet plays a crucial role, i.e. whether it is a singlet with each dot singly occupied or a singlet with only one dot doubly occupied. Depending on the type of singlet the qubit lifetimes change by several orders of magnitude. We also study the influence of a micromagnet, usually used in experiments to operate the qubit, on the relaxation time and decoherence time and present the regime where its effect is negligible. We suggest how to test experimentally our theory of one-phonon and two-phonon processes separately. We also show how the relaxation and decoherence time depend on different system parameters for S-T0 qubits. \n \nThe second part of the thesis is devoted to the other important constituent part of microsized devices, namely nanowires. We are interested in the dynamic of polarization of localized spins in the nanowires, as it can affect such important device characteristics as e.g. conductance. \n \nWe studied Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction-induced polarization in the nanowire in case when the voltage is applied to it. It was already proposed theoretically that in the ground state the localized spins in 1D systems align in a helix due to RKKY interaction. This polarization is still present until some critical temperature. The presence of such polarization acts as a spin filter for electrons, that most likely affects the conductance of the nanowire. Therefore we studied how this helical polarization changes when the voltage is applied. The key result is the appearance of the uniform polarization perpendicular to the helix plane, that occurs due to backscattering of electrons that is accompanied by flip-flop process with localized spins. When this uniform polarization is formed, the helix starts to rotate as a whole around the direction of the uniform polarization. We present the dependence of polarization of the localized spins on temperature and voltage. Remarkably the uniform polarization grows both with voltage and temperature in the given range of parameters. \n \nWe also considered the electron-induced relaxation of the nuclear spins. As the electron spins and nuclear spins interact via hyperfine interaction, the nuclear relaxation time reflects some properties of electron bath. Namely, we see a strong dependence of nuclear relaxation time on spin-orbit interaction strength. We present here the dependence of the nuclear relaxation time on the external magnetic field and chemical potential of the wire, that can be experimentally varied via gate. The dependences for the strong spin-orbit interaction and for the weak one are substantially different. Moreover, they have distinct peaks, that allow to get the value of spin-orbit interaction amplitude with the high precision.
Spin-lattice relaxation theory has been developed over almost a century, but some cardinal assumptions on the nature of the interactions involved have never been fully verified. This includes the weak coupling approximation, which makes it possible to describe spin dynamics perturbatively and leads to the canonical description of spin relaxation in terms of one- and two-phonon processes. Here, we extend the first-principles theory of spin relaxation to three-phonon processes and apply it to the vdW crystal of a spin-1/2 Chromium nitride complex. Results show that three-phonon contributions to spin relaxation only become relevant at temperatures inaccessible to experiments for this molecule, thus providing unprecedented evidence for the validity of the weak spin-phonon coupling assumption in spin relaxation theory. At the same time, we numerically show that a relatively small increase in spin-phonon coupling would lead to a crossover between three- and two-phonon processes' efficiency at room temperature, illustrating the possibility for three-phonon effects in molecular materials as well as paving the way to a systematic exploration of strong coupling in spin systems.