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.
Molecular spins offer promise in emerging quantum technologies such as quantum sensing and computing. At low temperatures, nuclear spin-spin interactions affect electron spin coherence lifetimes through pure dephasing. Nuclear-spin noise can originate from spin pairs within a molecule itself, pairs in a surrounding environment system, or pairs in which one spin is on the molecule and the other in the environment. Improving coherence times requires detailed knowledge of the dominant sources of dephasing. Here, we analyze the decoherence behavior of two molecular qubit candidates with various ligands and in different nuclear-spin containing solvents. We apply an electronic-structure enhanced, non-Markovian perturbative theoretical method to connect experimentally comparable dephasing times to individual spin pairs. This analysis allows the development of a computational workflow to strategically improve coherence lifetimes in spin systems where decoherence is dominated by spin-spin dephasing.
We solve the long-standing central spin problem for a general set of inhomogeneous bath couplings and a large class of initial bath states. We compute the time evolution of the coherence of a central spin coupled to a spin bath by resumming all orders of the time-convolutionless master equation, thus avoiding the need to assume weak coupling to the bath. The fully quantum, non-markovian solution is obtained in the large-bath limit and is valid up to a time scale set by the largest coupling constant. Our result captures the full decoherence of an electron spin qubit coupled to a nuclear spin bath in a GaAs quantum dot for experimentally relevant parameters. In addition, our solution is quite compact and can readily be used to make quantitative predictions for the decoherence process and to guide the design of nuclear state preparation protocols.
Molecular nanomagnets are quantum spin systems potentially serving as qudits for future quantum technologies thanks to their many accessible low-energy states. At low temperatures, the primary source of error in these systems is pure dephasing, caused by their interactions with the bath of surrounding nuclear spins degrees of freedom. Most importantly, as the system’s dimensionality grows going from qubits to qudits, the control and mitigation of decoherence become more challenging. Here, we analyze the characteristics of pure dephasing in molecular qudits under spin-echo sequences. We use a realistic description of their interaction with the bath, whose non-Markovian dynamics is accurately computed by the cluster correlation expansion technique. First, we show that the differences in the expectation values of the local spin operators on the eigenstates of the qudit are the source of decoherence in these systems. Indeed, we demonstrate that this is a necessary and sufficient condition to prevent the decay of coherence with time, also introducing a parameter to quantify the deviation from such ideal condition. We illustrate this with two paradigmatic systems: a single giant spin and a composite antiferromagnetic spin system. We then advance a proposal for optimized nanomagnets, identifying key ingredients for engineering robust qudits for quantum technologies.
We consider the buildup and decay of two-spin entanglement through phase interactions in a finite environment of surrounding spins, as realized in quantum computing platforms based on arrays of atoms, molecules, or nitrogen vacancy centers. The non-Markovian dephasing caused by the spin environment through Ising-type phase interactions can be solved exactly and compared to an effective Markovian treatment based on collision models. In a first case study on a dynamic lattice of randomly hopping spins, we find that non-Markovianity boosts the dephasing rate caused by nearest-neighbor interactions with the surroundings, degrading the maximum achievable entanglement. However, we also demonstrate that additional three-body interactions can mitigate this degradation, and that randomly timed reset operations performed on the two-spin system can help sustain a finite average amount of steady-state entanglement. In a second case study based on a model nuclear magnetic resonance system, we elucidate the role of bath correlations at finite temperature on non-Markovian dephasing. They speed up the dephasing at low temperatures while slowing it down at high temperatures, compared to an uncorrelated bath, which is related to the number of thermally accessible spin configurations with and without interactions.
Solid-state molecular qubits with open-shell ground states have great potential for addressability, scalability, and tunability, but understanding the fundamental limits of quantum coherence in these systems is challenging due to the complexity of the qubit environment. To address this, we develop a random Hamiltonian approach where the molecular
g-tensor fluctuates due to classical lattice motion obtained from molecular dynamics simulations at constant temperature. Atomistic
g-tensor fluctuations are used to construct Redfield quantum master equations that predict the relaxation
T1 and dephasing
T2 times of copper porphyrin qubits in a crystalline framework. Assuming one-phonon spin-lattice interaction processes,
1/T temperature scaling and
1/B3 magnetic field scaling of
T1 are established using atomistic bath correlation functions. Atomistic
T1 predictions overestimate the available experimental data by orders of magnitude. Quantitative agreement with measurements at all magnetic fields is restored by introducing a magnetic field noise model to describe lattice nuclear spins, with field-dependent noise amplitude in the range
δB∼10μT−1mT for the copper porphyrin system. We show that while
T1 scales as
1/B experimentally due to a combination of spin-lattice and magnetic noise contributions,
T2 scales strictly as $ 1/B^2$ due to low-frequency dephasing processes associated with magnetic field noise. Our work demonstrates the potential of dynamical methods for modeling the open quantum system dynamics of molecular spin qubits.
Predicting the quantum dynamics of promising solid-state and molecular quantum technology candidates remains a formidable challenge. Yet, accessing these dynamics is key to understanding and controlling decoherence mechanisms-a prerequisite for designing better qubits, sensors, and memories. We leverage a matrix product state representation to introduce a numerically exact and scalable method to achieve this goal. We demonstrate that our method accurately predicts coherence and population dynamics of spin networks across a wide range of parameter regimes, encompassing nuclear spin sensors and qubits in solid-state semiconductors and molecular magnets. Our method further predicts spin dynamics under the influence of repeated light pulses, which are commonly used to mitigate decoherence and perform quantum sensing experiments. Our method thus provides reliable results for moderately sized spin platforms spanning molecular magnets and solid-state spins that can guide the development of approximate but efficient quantum dynamics methods and enable principled inquiry into decoherence mechanisms.