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.
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 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.
Abstract Molecular Nanomagnets may enable the implementation of qudit-based quantum error-correction codes which exploit the many spin levels naturally embedded in a single molecule, a promising step towards scalable quantum processors. To fully realize the potential of this approach, a microscopic understanding of the errors corrupting the quantum information encoded in a molecular qudit is essential, together with the development of tailor-made quantum error correction strategies. We address these central points by first studying dephasing effects on the molecular spin qudit produced by the interaction with surrounding nuclear spins, which are the dominant source of errors at low temperatures. Numerical quantum error correction codes are then constructed, by means of a systematic optimization procedure based on simulations of the coupled system-bath dynamics, that provide a striking enhancement of the coherence time of the molecular computational unit. The sequence of pulses needed for the experimental implementation of the codes is finally proposed.
We consider pure dephasing of Bell states of electron spin qubits interacting with a sparse bath of nuclear spins. Using the newly developed two-qubit generalization of cluster-correlation expansion method, we calculate the spin-echo decay of $|\mathrm{\ensuremath{\Psi}}\ensuremath{\rangle}$ and $|\mathrm{\ensuremath{\Phi}}\ensuremath{\rangle}$ states for various interqubit distances. Comparing the results with calculations in which dephasing of each qubit is treated independently, we identify signatures of influence of common part of the bath on the two qubits. At large interqubit distances, this common part consists of many nuclei weakly coupled to both qubits, so that decoherence caused by it can be modeled by considering multiple uncorrelated sources of noise (clusters of nuclei), each of them weakly affecting the qubits. Consequently, the resulting genuinely two-qubit contribution to decoherence can be described as being caused by classical Gaussian noise. On the other hand, for small interqubit distances the common part of the environment contains clusters of spins that are strongly coupled to both qubits, and their contribution to two-qubit dephasing has visibly non-Gaussian character. We show that one can easily obtain information about non-Gaussianity of environmental noise affecting the qubits from the comparison of dephasing of $|\mathrm{\ensuremath{\Psi}}\ensuremath{\rangle}$ and $|\mathrm{\ensuremath{\Phi}}\ensuremath{\rangle}$ Bell states. Numerical results are obtained for two nitrogen vacancy centers interacting with a bath of
13C nuclei of natural concentration, for which we obtain that Gaussian description of a correlated part of environmental noise starts to hold for centers separated by about 3 nm.
There are several important solid-state systems, such as defects in solids, superconducting circuits and molecular qubits, for attractive candidates of quantum computations. Molecular qubits, which benefit from the power of chemistry for the tailored and inexpensive synthesis of new systems, face the challenge from decoherence effect. The decoherence effect is due to the molecular qubits' inevitable interactions to their environment. Strategies to overcome decoherence effect have been developed, such as designing a nuclear spin free environment and working at atomic clock transitions. These chemical approaches, however, have some fundamental limitations. For example, chemical approach restricts the ligand selection and design to ligands with zero nuclear magnetic dipole moment, such as carbon, oxygen, and sulfur. Herein, a physical approach, named Dynamical decoupling (DD), is utilized to combat decoherence, while the limitations of the chemical approaches can be avoided. The phase memory time
T2 for a transition metal complex has been prolonged to exceed one millisecond (
1.4 ms) by employing DD. The single qubit figure of merit $Q_M $ reaches $ 1.4\times 10^5$, which is
40 times better than that previously reported value for such system. Our results show that molecular qubits, with milliseconds
T2, are promising candidates for quantum information processing.
Molecular spins represent a versatile platform for quantum information science, with the potential to offer chemically tunable, addressable qubits. However, achieving this requires understanding and mitigating quantum decoherence. This Chapter provides a theoretical overview of current state-of-the-art chemical theory connecting ab initio electronic structure with open quantum system dynamics to guide the rational design of long-lived molecular qubits. Beginning at the electronic level, multi-reference and relativistic electronic structure methods to parameterize effective spin Hamiltonians are discussed, with a primary focus on accurately capturing
g-tensors, zero-field splitting, and hyperfine interactions. These parameters feed into models of spin-phonon and spin-spin coupling to quantify
T1 and
T2 relaxation across various environmental regimes. This Chapter evaluates a hierarchy of dynamical methods, ranging from factorization to matrix product state approaches, balancing computational cost against accuracy and generalizability. Ultimately, mapping these theoretical models to molecular architecture can establish design principles, such as isotopic substitution and spatial spin delocalization, to understand and extend coherence lifetimes.