arXiv subjects

Sonia Coriani

Publications and source records attributed to Sonia Coriani.

At least 19 recordsLinked to original sources

arXiv2026

Implementing QESEM's High-Accuracy Error Mitigation on a Quantum Computer: a Water Potential Energy Surface Study

Quantum error mitigation (QEM) is essential for extracting chemically accurate results from near-term quantum hardware. Many widely used QEM methods rely on uncontrolled heuristics whose bias depends on the specific circuit and noise realization. In this work, we employ QESEM---a characterization-based, unbiased quasi-probabilistic mitigation method---on IBM's Aachen quantum processor to compute the ground-state potential energy surface (PES) of the symmetrically-stretched water molecule. We consider a classically-optimized, single-layer perfect-pairing tiled unitary product state ansatz. We map this ansatz to an 8-qubit register corresponding to a (4,4) active space and the STO-3G basis set. Compared to the statevector reference, we find that raw QPU results typically overestimate the ground-state energy by around 500~mHa across the scanned geometries. On the other hand, QESEM-mitigated results fall approximately within 100~mHa, 30~mHa, or ``chemical accuracy'' ($\sim$1.5~mHa), depending on the target precision. We benchmark QESEM at both loose (0.1~Ha) and tight (0.01~Ha) precision targets, evaluating both individual and merged batches of runs. As the precision target is tightened, the accuracy improves systematically, matching or exceeding results reported in the literature. We further quantify the sampling cost of these results, reporting the number of shots required at each precision level. Our results show how, with the current levels of hardware error, reaching the highest accuracies demands substantial QPU time. The results demonstrate that the characterization-based, unbiased error mitigation provided by QESEM allows to measure quantitatively meaningful potential energy surfaces on current quantum hardware. Concurrently, they highlight the sampling overhead associated with QEM, which remains a central bottleneck en route to larger chemical problems and higher precision.

quant-ph↗

arXiv2026

Analytical Nuclear Gradients and Hessians on Quantum Hardware via Orbital-Optimized VQE with Error Mitigation

Nuclear gradients and Hessians are fundamental quantities in computational chemistry, essential for a wide range of applications including geometry optimization, vibrational spectroscopy, and molecular property calculations. In this work, we present their analytical implementation on quantum hardware. The methodology is formulated within an active-space framework combining orbital optimization and linear-response theory. On the quantum-computing side, the approach employs the tiled unitary product state (tUPS) ansatz to directly evaluate the tensor elements required for solving the response equations. Moreover, the expectation values are corrected using an adapted confusion-matrix error-mitigation scheme in combination with post-selection criteria. The resulting workflow is assessed on molecular hydrogen and on water through the calculation of potential energy surfaces, nuclear gradients, Hessians, and vibrational frequencies, enabling the evaluation of both its capabilities and current limitations. The results demonstrate good performance for the hydrogen molecule, whereas the water molecule provides a more demanding test of quantum-hardware resources and highlights the trade-offs associated with error-mitigation strategies. The quantified analysis of the results identify the main sources of errors, suggesting improvement directions for more accurate quantum computer applications.

physics.chem-ph↗

arXiv2026

Orbital-optimized spin-adapted multistate contracted VQE for excited states and properties on quantum hardware

We introduce the orbital-optimized multistate contracted variational quantum eigensolver (oo-MC-VQE) method with spin-adapted operators for the computation of ground and excited states, as well as state-specific and transition properties. The use of spin-adapted operators ensures that the spin symmetry of the reference states is conserved throughout the VQE optimization. In multistate variational approaches, achieving a balanced description of an increasing number of electronic states places growing demands on the expressibility of the underlying ansatz, thereby introducing a fundamental trade-off between accuracy and circuit complexity. We consider the effects of this trade-off explicitly and find that the number of circuit parameters required to obtain accurate results is reported to scale approximately linearly in the number of states. We further present an explicit quantum-circuit implementation of the oo-MC-VQE method and demonstrate its integration with quantum error mitigation techniques. Finally, we execute the method on real quantum devices to compute absorption spectra for two benchmark molecular systems.

quant-ph↗

arXiv2026

Resource-efficient energy-based operator selection in fermionic ADAPT-VQE via exact Hamiltonian transformation

The energy-based approach to operator selection in ADAPT-VQE relies on reconstructing the one-parameter energy landscape for each operator in the pool. In fermionic implementations, the cost of reconstructing this energy landscape often becomes a bottleneck. We address this issue through an exact Hamiltonian transformation that reformulates the one-parameter energy landscape according to a generator-dependent fragmentation of the transformed Hamiltonian. While our method is mathematically identical to standard fermionic Rotoselect, it effectively reduces its cost by about a factor of two, bringing it close to that of gradient-based ADAPT-VQE. We use this formulation to benchmark the gradient-based and energy-based selection approaches in combination with two ansatz-optimization strategies -- "last", where only the appended operator is optimized, and "full", where the full ansatz is re-optimized -- and with both fixed-orbital and orbital-optimized formulations. The benchmark comprises $\text{LiH}$, $\text{BeH}_2$, and $\text{H}_2\text{O}$ at both equilibrium and stretched geometries. In the most weakly correlated system, pairing energy-based selection with "last" optimization enables the efficient construction of an accurate ansatz, which avoids any VQE optimization. As correlation increases, full ansatz re-optimization and orbital optimization become the main factors governing convergence and overall resource cost. This study shows how exact Hamiltonian transformations provide an effective route to reducing the measurement overhead of fermionic energy-based ADAPT-VQE. Moreover, the benchmark clarifies the relative role of operator scoring approach, re-optimization strategy, and orbital treatment in the performance of ADAPT-VQE.

quant-ph↗

arXiv2026

Velocity Formulations for Hyper-Rayleigh Scattering Optical Activity Spectroscopy: Addressing the Origin-dependence Problem

The theory of hyper-Rayleigh scattering optical activity (HRS-OA) spectroscopy has previously been described within the length formulation of the pure electric-dipole and mixed (electric-dipole/magnetic-dipole and electric-dipole/electric-quadrupole) first hyperpolarizabilities required for the description of this process. In this work, we provide an alternative formulation of these pure and mixed hyperpolarizabilities. This new formulation made use of the velocity form of the electric-dipole and electric-quadrupole moment operators that enter in the quadratic response functions. A one-to-one correspondence is found for the gauge-origin shifts obtained in the two formulations. These relations ensure the origin-independence of the theory also for the velocity formulation. Furthermore, even though the basis set dependence of the velocity formulation is more significant compared to the length one, the former is origin-independent by design. This property makes it particularly suitable for calculations of HRS-OA invariants using approximated (variational or not) wavefunctions.

physics.chem-ph↗

arXiv2026

Second-Order Magnetic Properties in Paramagnetic Molecules From a Current Density Formulation Including Scalar Relativistic Effects

This work presents the theoretical background for the computation of nuclear magnetic shielding, nuclear hyperfine and magnetizability tensors of paramagnetic molecules, using a magnetically induced current density framework to account for both orbital and spin contributions. The resulting magnetizability tensor is fully consistent with the general Van Vleck formulation, recovering the temperature-dependent Curie contribution through the explicit integration of the magnetically induced spin current density. The methodology proposed herein provides a straightforward computational route that bypasses the complex evaluation of g-tensors and Zero-Field Splitting (ZFS) Hamiltonians. While the theoretical framework is general, we present applications rooted on physically motivated approximations where scalar relativistic effects are incorporated through corrections based on the Zeroth-Order Regular Approximation (ZORA) Hamiltonian within the ground-state spin density. This approach combines a relativistic self-consistent field (SCF) calculation for the ground-state spin density with a non-relativistic, origin-independent current density calculation for the orbital contribution. This hybrid strategy is shown to capture the Heavy-Atom Light-Atom (HALA) effect in 1H and 13C shieldings, particularly in paramagnetic molecular systems containing transition metals up to the 3d series. By restricting the relativistic treatment to the spin density, where scalar relativistic effects are dominant, and neglecting such effects on the orbital contribution of light atoms, this method offers a good compromise between computational efficiency and accuracy for the characterization of large open-shell molecular systems.

quant-ph↗

arXiv2026

A Lanczos-based algorithm for sum-over-states calculations of NMR spin--spin coupling constants at the RPA level of theory: The Fermi-contact term

The analysis of nuclear magnetic resonance parameters, such as the indirect nuclear spin-spin coupling constants, in terms of contributions from localised molecular orbitals is a commonly used approach for gaining a deeper understanding of experimentally observed trends in these parameters. In the vast majority of these studies, contributions from pairs of one occupied and one virtual orbital are calculated and analyzed. Analyses in terms of two pairs of an occupied and a virtual orbital, that would allow for the study of coupling pathways, are much more seldom, as they require calculating the coupling constants as a sum over all excited states. Previous studies have shown that, for the often dominating Fermi-contact contribution to the coupling constants, more or less all excited states have to be calculated when employing a Davidson algorithm, because the most high-lying excited states can also make a significant contribution to the Fermi-contact term. In this study we investigated therefore, whether by employing a Lanczos algorithm one can obtain converged values of the Fermi-contact contribution to the indirect nuclear spin-spin coupling constants already with a significantly smaller percentage of the total number of excited states included in the sum-over-states expression. To this purpose we have extended the recent implementation of a Lanczos algorithm for the RPA/TDHF or TDDFT eigenvalue problem in the Dalton program (L. Zamok et al. J. Chem. Phys. 156, 014102 (2022)). The new procedure was tested on 17 molecules containing first, second and third row atoms. We find that, for most coupling constants, less than 50% of the excited pseudo states are necessary for converging the Fermi-contact term with an error of less than 0.5 Hz. For the few exceptions, typically for molecules with third-row atoms, around 60% were necessary.

physics.chem-ph↗

arXiv2026

The X-ray absorption spectrum of the propargyl radical, C$_3$H$_3^{\cdot}$

We report a combined experimental and computational study of the near-edge X-ray absorption fine structure (NEXAFS) spectrum of the propargyl radical, C$_3$H$_3^{\cdot}$. As a central intermediate in the formation of polycyclic aromatic hydrocarbons, the propargyl radical is a species of considerable relevance in combustion and astrochemistry and was here generated by pyrolysis from propargyl bromide. The NEXAFS spectrum shows a pronounced band at 282.2 eV corresponding to transitions from carbon 1s orbitals to singly occupied molecular orbitals. Ab initio calculations show that two transitions to the lowest lying states 1 $^2$A$_1$ and 2 $^2$A$_1$, which take place from the C1s orbital of the two terminal carbon atoms, contribute to this band. In addition, a 420 meV spacing of the first band is visible and is assigned to a vibrational progression in the symmetric CH$_2$ stretch. Transitions at higher energies are also described reasonably well by theory. The fragmentation pattern was investigated at the different resonant transitions and shows the cleavage of one as well as both C--C bonds.

physics.chem-ph↗

arXiv2025

Cost-effective scalable quantum error mitigation for tiled Ans\"atze

We introduce a cost-effective quantum error mitigation technique that builds upon the recent Ansatz-based gate and readout error mitigation method (M0). The technique, tiled M0, leverages the unique structure of tiled Ans\"atze (e.g., tUPS, QNP, hardware-efficient circuits) to apply a locality approximation to M0 that results in an exponential reduction in the QPU cost of the noise characterization. We validate the technique for molecular ground state energy calculations with the tUPS Ansatz on LiH, molecular hydrogen, water, butadiene, and benzene (4-12 qubits), demonstrating little to no loss in accuracy compared to M0 in noisy simulations. We also show the performance of the technique in quantum experiments, highlighting its potential use in near-term applications.

quant-ph↗

arXiv2025

Orbital-Optimized Unitary Coupled Cluster for Indirect Nuclear Spin-Spin Coupling Constants within a Quantum Linear Response Framework

We present a quantum linear response (qLR) approach within an active-space framework for computing indirect nuclear spin-spin coupling constants, a key ingredient in NMR spectra predictions. The method employs the unitary coupled cluster (UCC) ansatz and its orbital-optimized variant (ooUCC), both suitable for quantum computing implementations, to evaluate spin-spin coupling constants via qLR. Test calculations on five small molecules are compared with CASCI, CASSCF, and conventional CCSD results. qLR with UCC/ooUCC yields spin-spin coupling constants comparable to classical methods. We further examine the role of orbital optimization and find that ooUCC markedly affects the computed couplings; orbital-optimized results show better agreement with CCSD. These findings indicate that orbital optimization is important for accurate NMR coupling predictions within quantum-computing-friendly correlated methods.

physics.chem-ph↗

arXiv2025

Quantum error mitigation using energy sampling and extrapolation enhanced Clifford data regression

Error mitigation is essential for the practical implementation of quantum algorithms on noisy intermediate-scale quantum (NISQ) devices. This work explores and extends Clifford Data Regression (CDR) to mitigate noise in quantum chemistry simulations using the Variational Quantum Eigensolver (VQE). Using the H$_4$ molecule with the tiled Unitary Product State (tUPS) ansatz, we perform noisy simulations with the ibm torino noise model to investigate in detail the effect of various hyperparameters in CDR on the error mitigation quality. Building on these insights, two improvements to the CDR framework are proposed. The first, Energy Sampling (ES), improves performance by selecting only the lowest-energy training circuits for regression, thereby further biasing the sample energies toward the target state. The second, Non-Clifford Extrapolation (NCE), enhances the regression model by including the number of non-Clifford parameters as an additional input, enabling the model to learn how the noisy-ideal mapping evolves as the circuit approaches the optimal one. Our numerical results demonstrate that both strategies outperform the original CDR.

quant-ph↗

arXiv2025

eT 2.0: An efficient open-source molecular electronic structure program

The eT program is an open-source electronic structure program with emphasis on performance and modularity. As its name suggests, the program features extensive coupled cluster capabilities, performing well compared to other electronic structure programs, and, in some cases, outperforming commercial alternatives. However, eT is more than a coupled cluster program; other models based on wave function theory (such as full and reduced space configuration interaction and a variety of self-consistent field models) and density functional theory are supported. The second major release of the program, eT 2.0, has specialized functionality for strong light-matter coupling conditions. In addition, it includes a wide range of optimizations and algorithmic improvements, as well as new capabilities for exploring potential energy surfaces and for modeling experiments in the UV and X-ray regimes. Molecular gradients are now available at the coupled cluster level, and high-accuracy spectroscopic simulations are available at reduced computational cost within the multilevel coupled cluster and multiscale frameworks. We present the modifications to the program since its first major release, eT 1.0, highlighting some notable new features and demonstrating the performance of the new version relative to the first release and to other established electronic structure programs.

physics.chem-ph↗

arXiv2025

Tracking photophysical relaxation in spiropyran with simulated time-resolved X-ray absorption spectroscopy

Spiropyran is a prototype photoswitch that undergoes photoinduced ring-opening via C-O bond fission. The quantum yield for this photochemical reaction is low, with photophysical relaxation being the dominant process. Previous theoretical studies have suggested that photophysical relaxation proceeds via cleavage and subsequent reformation of a C-N bond. However, experimental evidence for this mechanism is lacking; most time-resolved studies have probed in the ultraviolet-visible domain, where C-N bond fission is unlikely to leave clear signatures. Here, we use non-adiabatic dynamics simulations in conjunction with X-ray absorption spectroscopic calculations to investigate the possibility of tracking the photophysical relaxation in spiropyran with time-resolved X-ray absorption spectroscopy at the nitrogen K-edge. The simulations predict that cleavage of the C-N bond results in a transient red-shift of the X-ray absorption. These results indicate a potential experimental route to gain a mechanistic understanding of the efficient photophysical relaxation that limits the efficiency of spiropyran-based photochromic systems.

physics.chem-ph↗

arXiv2025

Reduced density matrix and cumulant approximations of quantum linear response

Linear response (LR) is an important tool in the computational chemist's toolbox. It is therefore no surprise that the emergence of quantum computers has led to a quantum version, quantum LR (qLR). However, the current quantum era of near-term intermediary scale quantum (NISQ) computers is dominated by noise, short decoherence times, and slow measurement speed. It is therefore of interest to find approximations that greatly reduce the quantum workload while only slightly impacting the quality of a method. In an effort to achieve this, we approximate the naive qLR with singles and doubles (qLRSD) method by either directly approximating the reduced density matrices (RDMs) or indirectly through their respective reduced density cumulants (RDCs). We present an analysis of the measurement costs behind qLR with RDMs, and report qLR results for model Hydrogen ladder systems; for varying active space sizes of OCS, SeH$_2$, and H$_2$S; and for symmetrically stretched H$_2$O and BeH$_2$. Discouragingly, while approximations to the 4-body RDMs and RDCs seem to produce good results for systems at the equilibrium geometry and for some types of core excitations, they both tend to fail when the system exhibits strong correlation. All approximations to the 3-body RDMs and/or RDCs severely affect the results and cannot be applied.

physics.chem-ph↗

arXiv2025

Shake-down spectroscopy as state- and site-specific probe of ultrafast chemical dynamics

Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS$_2$ molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the pre-dissociation dynamics is controversial. We present XPS spectra from photoexcited CS$_2$, obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the pre-dissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the pre-dissociation dynamic pathway.

physics.chem-ph↗

arXiv2025

Redundant parameter dependencies in truncated classic and quantum Linear Response and Equation of Motion theory

Extracting molecular properties from a wave function can be done through the linear response (LR) formalism or, equivalently, the equation of motion (EOM) formalism. For a simple model system, He in a 6-31G basis, it is here shown that calculated excitation energies depend on the specifically chosen orbitals, even when the ground-state is the FCI solution, if the LR is truncated to a singles expansion. This holds for naive, projected, self-consistent, and state-transfer parametrizations of the LR operators. With a focus on the state-transfer parameterization, this problem is shown to also hold for more complicated systems, and is also present when the LR is truncated to singles and doubles. This problem can be alleviated by performing a ground-state constrained trace optimization of the Hessian matrix before performing the LR calculation. It is finally shown that spectra can be further improved for small LR expansions by targeting only a few states in the constrained trace optimization using constrained state-averaged UCC.

physics.chem-ph↗

arXiv2025

Exact closed-form expression for unitary spin-adapted fermionic singlet double excitation operators

We derive exact closed-form expressions for the matrix exponential of the anti-Hermitian spin-adapted singlet double excitation fermionic operators. These expressions enable the efficient implementation of such operators within unitary product state frameworks targeting conventional hardware, and allow for the implementation of ansatze that guarantee convergence to specific spin symmetries. Moreover, these exact closed-form expressions might also lay the groundwork for constructing spin-adapted circuits for quantum devices.

quant-ph↗

arXiv2025

Unraveling the relaxation dynamics of Uracil: insights from time-resolved X-ray photoelectron spectroscopy

We report a study of the electronic and nuclear relaxation dynamics of the photoexcited RNA base uracil in the gas phase, using time-resolved core level photoelectron spectroscopy together with high level calculations. The dynamics was investigated by trajectory surface-hopping calculations, and the core ionization energies were calculated for geometries sampled from these. The molecule was excited by a UV laser and dynamics was probed on the oxygen, nitrogen and carbon site by core electron spectroscopy. Assuming a particular model, we find that the initially excited $S_2(\pi\pi^*)$ state of uracil decays with a time constant of 17 $\pm$ 4 fs to the ground state directly, or to the $S_1(n\pi^*)$ state via internal conversion. We find no evidence that the $S_1(n\pi^*)$ state decays to the ground state by internal conversion; instead it decays to triplet states with a time constant of 1.6 $\pm$ 0.4 ps. Oscillations of the $S_1(n\pi^*)$ state O 1s intensity as a function of time correlate with those of calculated C4=O8 and C5=C6 bond lengths, which undergo a sudden expansion following the initial $\pi \to \pi^*$ excitation. We also observe oscillations in the mean energy of the main line (core ionized ionic state), which we tentatively assign to dynamics of the hot ground state. Our calculations support our interpretation of the data, and provide detailed insight into the relaxation processes of uracil.

physics.chem-ph↗