arXiv subjects

Alessandro Chiesa

Publications and source records attributed to Alessandro Chiesa.

At least 19 recordsLinked to original sources

arXiv2026

Electron-electron interactions mediated by overdamped vibrations: Implications for chirality-induced spin selectivity

Motivated by chirality-induced spin selectivity (CISS), we investigate spin polarization during molecular electron transfer through a correlated bridge in the presence of a rapidly relaxing Peierls mode. By modulating both electronic hopping and spin--orbit coupling, the mode mediates two-body spin-spin interactions, including isotropic, anisotropic, and Dzyaloshinskii-Moriya exchange. We derive these interactions using an exact Lang-Firsov transformation for a four-site chiral bridge. We then include fast vibrational relaxation in the joint electron--vibration master equation and derive the reduced electronic dynamics to second order in the vibronic coupling, retaining both coherent and dissipative contributions and the finite-time buildup of the vibrational response. We test our derivation by numerical simulations, finding spin polarization accumulated at the acceptor after unpolarized injection, with nonmonotonic dependence on damping and bridge filling. Within the postulated local-loss model, our results show that rapid vibrational relaxation does not preclude spin polarization through a correlated bridge and provide a framework for assessing vibration-mediated interactions and dissipative dynamics as ingredients of CISS in molecular electron transfer.

cond-mat.str-el↗

arXiv2026

Beyond Pure Dephasing: Quantum Error Correction in Single Molecules Requires Multiple Spins

We propose multi-spin molecules as a viable architecture for fault-tolerant quantum computing. To this aim, we introduce a correction protocol handling both diagonal and off-diagonal errors, typically associated with dephasing and relaxation. The scheme is based on a hybrid encoding which combines dephasing-tolerant units suppressing the leading pure dephasing error into a multi-spin molecule implementing a multi-qubit code for residual off-diagonal errors. Our proposal leverages peculiar properties of molecular spins, i.e. the strong hierarchy between different errors and the possibility to engineer multi-spin molecules at the synthetic level. Moreover, it addresses the important issue of the loss of coherences in anharmonic systems subject to off-diagonal errors, which hampers their correction at the single spin level. Thanks to the huge suppression of dephasing by the first-level code, we numerically demonstrate the potential performance of this strategy even with a limited number of spins per logical unit.

cond-mat.mes-hall↗

arXiv2026

EPR as a probe for the mechanisms of chirality-induced spin selectivity in photoinduced charge transfer

Several models for chirality-induced spin selectivity (CISS) in charge transfer have been proposed, but rarely compared directly with experiments. This step is essential for their validation and future progress of the field. Here we investigate a broad class of radical pair states associated with different microscopic models by computing the related electron-paramagnetic resonance spectra. This allows us to evidence peculiar signatures of different radical pair states, to study their experimental accessibility and identify conditions to verify proposed microscopic models.

cond-mat.mes-hall↗

arXiv2026

Succinct Arguments for QMA in the Quantum Random Oracle Model

Succinct arguments are a fundamental cryptographic primitive for verifying computational claims with small communication. In the classical setting, succinct arguments for NP can be constructed from unstructured hardness alone (e.g., hash functions) by compiling probabilistically checkable proofs (PCPs) or interactive oracle proofs (IOPs) for NP via the commit-and-open paradigm. In contrast, known succinct arguments for QMA rely on ``structured'' cryptographic primitives, or on the quantum PCP conjecture. We construct the first succinct argument for QMA in the quantum random oracle model (QROM) without relying on additional cryptographic assumptions or unproven conjectures. This yields succinct arguments for QMA from unstructured hardness alone, showing that ideal hash functions not only suffice for succinct arguments for NP but also for QMA. Underlying our result is an efficiency-preserving transformation that compiles quantum interactive oracle proofs (QIOPs), a recently introduced interactive generalization of quantum PCPs, into quantum arguments for the same language, via a natural quantum commit-and-open paradigm. Our transformation applies to every QIOP with public-query soundness, a notion that we formalize to capture a natural requirement of the commit-and-open paradigm and is satisfied by a known QIOP for QMA. As a key ingredient in our transformation, we formalize and construct extractable vector commitments for quantum states with local openings in the QROM, which may be of independent interest.

quant-ph↗

arXiv2026

Can AI Oversight Be Zero Knowledge?

AI systems increasingly produce outputs from confidential data, such as a fitness-for-duty assessment from medical records or the predicted properties of a drug candidate from its secret structure. It is important to verify that such outputs are correct without revealing the underlying data. A recent line of work studies verification of AI outputs via interactive proofs and debate for oracle-aided computation, where correctness may depend on an oracle such as human judgment, a physical experiment, or the web. These works focus on verification by a verifier that runs much faster than the computation. However, such efficient verification is impossible for general oracle-aided computation, and these works therefore rely on additional assumptions. We focus instead on privacy: allowing the verifier to run in time polynomial in the computation, we ask whether interactive arguments for oracle-aided computation can be zero knowledge, so that the verifier learns nothing about the confidential data beyond the correctness of the output. We prove that, in general, they cannot. In the random oracle model, there are no zero-knowledge proofs for all oracle-aided computations, even if both the prover and the verifier are allowed to run much longer than the computation itself. The impossibility extends to debate, a canonical model for scalable oversight. On the positive side, we show that if the oracle attaches a cryptographic signature to each of its answers, then every oracle-aided computation can be verified in zero knowledge with an efficient prover and verifier, assuming only collision-resistant hash functions. Beyond privacy, this also gives an alternative approach to scalable oversight that relies neither on an honest opponent, as in debate, nor on the robustness of the computation, as in prior single-prover protocols.

cs.AI↗

arXiv2026

Vibrationally-mediated Dzyaloshinskii-Moriya interaction as the origin of Chirality-Induced Spin Selectivity in donor-acceptor molecules

Chirality-induced spin selectivity (CISS) was recently observed in photo-excited donor-chiral bridge-acceptor molecules, but a predictive theory able to explain available experiments is still lacking. Here we show that low-energy torsional modes modulating hopping and spin-orbit coupling give rise to a Dzyaloshinskii-Moriya interaction between the transferred electron and the one sitting on the donor, producing high spin polarization for perfectly realistic parameters. Our model introduces a low energy scale in the spin dynamics which explains the magnetic field dependence observed in EPR measurements and predicts a non-trivial temperature dependence, as demonstrated by numerical simulations. The present theory lays the foundations for future test-bed experiments and for the design of applications in spintronics and quantum technologies.

cond-mat.mes-hall↗

arXiv2025

Quantum Rewinding for IOP-Based Succinct Arguments

We analyze the post-quantum security of succinct interactive arguments constructed from interactive oracle proofs (IOPs) and vector commitment schemes. We prove that an interactive variant of the BCS transformation is secure in the standard model against quantum adversaries when the vector commitment scheme is collapsing. Our proof builds on and extends prior work on the post-quantum security of Kilians succinct interactive argument, which is instead based on probabilistically checkable proofs (PCPs). We introduce a new quantum rewinding strategy that works across any number of rounds. As a consequence of our results, we obtain standard-model post-quantum secure succinct arguments with the best asymptotic complexity known.

cs.CR↗

arXiv2025

Dephasing-tolerant quantum sensing for transverse magnetic fields with spin qudits

We propose a dephasing-tolerant protocol for quantum sensing of transverse magnetic fields which exploits spin qudit sensors with embedded fault-tolerant (FT) quantum error correction. By exploiting longitudinal drives, the transverse field induces logical Rabi oscillations between encoded states, whose frequency is linear in the transverse field to be probed. Numerical simulations show that the present FT protocol enables the detection of very small fields, orders of magnitudes below the limit imposed by the coherence time.

quant-ph↗

arXiv2024

Quantum Information Processing with Molecular Nanomagnets: an introduction

Many problems intractable on classical devices could be solved by algorithms explicitly based on quantum mechanical laws, i.e. exploiting quantum information processing. As a result, increasing efforts from different fields are nowadays directed to the actual realization of quantum devices. Here we provide an introduction to Quantum Information Processing, focusing on a promising setup for its implementation, represented by molecular spin clusters known as Molecular Nanomagnets. We introduce the basic tools to understand and design quantum algorithms, always referring to their actual realization on a molecular spin architecture. We then examine the most important sources of noise in this class of systems and then one of their most peculiar features, i.e. the possibility to exploit many (more than two) available states to encode information and to self-correct it from errors via proper design of quantum error correction codes. Finally, we present some examples of quantum algorithms proposed and implemented on a molecular spin qudit hardware.

quant-ph↗

arXiv2024

Room-temperature optical spin polarization of an electron spin qudit in a vanadyl -- free base porphyrin dimer

Photoexcited organic chromophores appended to molecular qubits can serve as a source of spin initialization or multi-level qudit generation for quantum information applications. So far, this approach has been primarily investigated in chromophore/stable radical systems. Here, we extend this concept to a meso-meso linked oxovanadium(IV) porphyrin - free base porphyrin dimer. Femtosecond transient absorption experiments reveal that photoexcitation of the free base porphyrin leads to picosecond triplet state formation via enhanced intersystem crossing. Time-resolved electron paramagnetic resonance (TREPR) experiments carried out at both 85 K and room temperature reveal the formation of a long-lived spin-polarized quartet state through triplet-doublet spin mixing. Notably, a distinct hyperfine structure arising from the interaction between the electron spin quartet state and the vanadyl nucleus (51V, I=7/2) is evident, with the quartet state exhibiting long-lived spin polarization even at room temperature. Theoretical simulations of the TREPR spectra confirm the photogenerated quartet state and provide insights into the non-Boltzmann spin populations. Exploit-ing this phenomenon affords the possibility of using photoinduced triplet states in porphyrins for quantum information as a resource to polarize and magnetically couple molecular electronic or nuclear spin qubits and qudits.

quant-ph↗

arXiv2023

Fault-Tolerant Computing with Single Qudit Encoding

We discuss stabilizer quantum-error correction codes implemented in a single multi-level qudit to avoid resource escalation typical of multi-qubit codes. These codes can be customized to the specific physical errors on the qudit, effectively suppressing them. We demonstrate a Fault-Tolerant implementation on molecular spin qudits, showcasing nearly exponential error suppression with only linear qudit size growth. Notably, this outperforms qubit codes using thousands of units. We also outline the required properties for a generic physical system to Fault-Tolerantly implement these embedded codes.

quant-ph↗

arXiv2023

Direct Observation of Chirality-Induced Spin Selectivity in Electron Donor-Acceptor Molecules

The role of chirality in determining the spin dynamics of photoinduced electron transfer in donor-acceptor molecules remains an open question. Although chirality-induced spin selectivity (CISS) has been demonstrated in molecules bound to substrates, experimental information about whether this process influences spin dynamics in the molecules themselves is lacking. Here we use time-resolved electron paramagnetic resonance spectroscopy to show that CISS strongly influences the spin dynamics of isolated covalent donor-chiral bridge-acceptor (D-B$χ$-A) molecules in which selective photoexcitation of D is followed by two rapid, sequential electron transfer events to yield D$^+$-B$χ$-A$^-$. Exploiting this phenomenon affords the possibility of using chiral molecular building blocks to control electron spin states in quantum information applications.

cond-mat.mes-hall↗

arXiv2023

Proof-of-concept Quantum Simulator based on Molecular Spin Qudits

The use of $d$-level qudits instead of two-level qubits can largely increase the power of quantum logic for many applications, ranging from quantum simulations to quantum error correction. Molecular Nanomagnets are ideal spin systems to realize these large-dimensional qudits. Indeed, their Hamiltonian can be engineered to an unparalleled extent and can yield a spectrum with many low-energy states. In particular, in the last decade intense theoretical, experimental and synthesis efforts have been devoted to develop quantum simulators based on Molecular Nanomagnets. However, this remarkable potential is practically unexpressed, because no quantum simulation has ever been experimentally demonstrated with these systems. Here we show the first prototype quantum simulator based on an ensemble of molecular qudits and a radiofrequency broadband spectrometer. To demonstrate the operativity of the device, we have simulated quantum tunneling of the magnetization and the transverse-field Ising model, representative of two different classes of problems. These results represent an important step towards the actual use of molecular spin qudits in quantum technologies.

quant-ph↗

arXiv2023

Universal qudit gate synthesis for transmons

Gate-based quantum computers typically encode and process information in two-dimensional units called qubits. Using $d$-dimensional qudits instead may offer intrinsic advantages, including more efficient circuit synthesis, problem-tailored encodings and embedded error correction. In this work, we design a superconducting qudit-based quantum processor wherein the logical space of transmon qubits is extended to higher-excited levels. We propose a universal gate set featuring a two-qudit cross-resonance entangling gate, for which we predict fidelities beyond $99\%$ in the $d=4$ case of ququarts with realistic experimental parameters. Furthermore, we present a decomposition routine that compiles general qudit unitaries into these elementary gates, requiring fewer entangling gates than qubit alternatives. As proof-of-concept applications, we numerically demonstrate the synthesis of ${\rm SU}(16)$ gates for noisy quantum hardware and an embedded error correction sequence that encodes a qubit memory in a transmon ququart to protect against pure dephasing noise. We conclude that universal qudit control -- a valuable extension to the operational toolbox of superconducting quantum information processing -- is within reach of current transmon-based architectures and has applications to near-term and long-term hardware.

quant-ph↗

arXiv2022

Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge

It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential for several aspects of quantum information science, e.g., the optical control and readout of qubits. In this context, the direct observation of this phenomenon via spin-sensitive spectroscopies is of utmost importance to establish future guidelines to control photo-driven spin selectivity in chiral structures. Here, we provide direct proof that time-resolved electron paramagnetic resonance (EPR) can be used to detect long-lived spin polarization generated by photoinduced charge transfer through a chiral bridge. We propose a system comprising CdSe QDs, as a donor, and C60, as an acceptor, covalently linked through a saturated oligopeptide helical bridge (\c{hi}) with a rigid structure of ~ 10Å. Time-resolved EPR spectroscopy shows that the charge transfer in our system results in a C60 radical anion, whose spin polarization maximum is observed at longer times with respect to that of the photogenerated C60 triplet state. Notably, the theoretical modeling of the EPR spectra reveals that the observed features may be compatible with chirality-induced spin selectivity and identifies which parameters need optimization for unambiguous detection of the phenomenon. This work lays the basis for the optical generation and direct manipulation of spin polarization induced by chirality.

physics.chem-ph↗

arXiv2021

Counteracting dephasing in Molecular Nanomagnets by optimized qudit encodings

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 optimisation 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.

quant-ph↗

arXiv2021

Post-Quantum Succinct Arguments: Breaking the Quantum Rewinding Barrier

We prove that Kilian's four-message succinct argument system is post-quantum secure in the standard model when instantiated with any probabilistically checkable proof and any collapsing hash function (which in turn exist based on the post-quantum hardness of Learning with Errors). This yields the first post-quantum succinct argument system from any falsifiable assumption. At the heart of our proof is a new quantum rewinding procedure that enables a reduction to repeatedly query a quantum adversary for accepting transcripts as many times as desired. Prior techniques were limited to a constant number of accepting transcripts.

cs.CR↗

arXiv2021

Molecular spin qudits for quantum simulation of light-matter interactions

We show that molecular spin qudits provide an ideal platform to simulate the quantum dynamics of photon fields strongly interacting with matter. The basic unit of the proposed molecular quantum simulator can be realized by a simple dimer of a spin 1/2 and a spin $S$ transition metal ion, solely controlled by microwave pulses. The spin $S$ ion is exploited to encode the photon field in a flexible architecture, which enables the digital simulation of a wide range of spin-boson models much more efficiently than by using a multi-qubit register. The effectiveness of our proposal is demonstrated by numerical simulations using realistic molecular parameters, whose prerequisites delineating possible chemical approaches are also discussed.

quant-ph↗