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Mario Ruben

Publications and source records attributed to Mario Ruben.

At least 19 recordsLinked to original sources

Controlled ion-ion interactions and cavity-enhanced emission of a coherent dinuclear Eu$^{3+}$ complex

Molecular rare-earth-ion complexes offer unique opportunities for quantum technologies by combining the intrinsic coherence properties of rare-earth ions with chemically tunable molecular environments. A crucial capability is the realization of multi-qubit architectures with defined qubit couplings to enable two-qubit quantum gates. Here, we investigate the optical coherence properties and excitation-induced interactions of two Eu$^{3+}$-based molecular complexes, comparing a mononuclear reference system with a dinuclear analogue in which two Eu$^{3+}$ ions are positioned at a well-defined intramolecular distance of about 7 Angstrom. Using cryogenic ensemble spectroscopy, including spectral hole burning, free-induction decay, and photon echo measurements at temperatures down to 100 mK, we demonstrate long optical coherence times $T_{2,\text{o}}$ of up to 9 $\mu$s. As a key step toward scalable multi-qubit architectures, a control-target sequence was implemented to probe conditional ion-ion interactions, revealing a stronger interaction-induced dephasing in the dinuclear complex. Finally, we show the integration of the dinuclear complex into a fiber-based optical microcavity, and observe an 380-fold emission enhancement of the $\mathrm{}^5\mathrm{D}_0\rightarrow\mathrm{}^7\mathrm{F}_0$ transition. Together, these results position molecular rare-earth complexes as versatile and chemically tunable building blocks for scalable quantum technologies.

quant-ph

Fast Nuclear Spin Read-Out in Single Molecule Magnets

Nuclear spins in 4f single-molecule magnets (SMMs) are promising qubits or qudits candidates for quantum information processing due to their relative isolation and reduced susceptibility to environmental disturbances, while their hyperfine coupling to the 4f magnetic moments enable readout and control. So far, the nuclear spin states of individual TbPc2 SMMs have been detected in transport measurements via the spin-cascade effect. Here, we demonstrate a fast, field-sweep-free readout of nuclear spin in individual 163DyPc2 (I = 5/2) and 159TbPc2 (I = 3/2) using millikelvin spin-polarized scanning tunneling microscopy. This fast readout is enabled by the hyperfine interactions, which modifies the statistics of the telegraph noise generated by reversals of the Ln3+ moment, thereby revealing the nuclear spin state. We observe nuclear spin relaxation times T1 in excess of minutes. Furthermore, we drive nuclear spin transitions using a radio-frequency field and detect the resulting nuclear magnetic resonance directly in the tunneling current. Thus our approach enables fast access to long-lived nuclear spin states in an individual molecule

cond-mat.mes-hall

Photophysical properties of Eu3+ complexes approaching electronic contact to a metal surface

The application of rare-earth complexes in electrically driven light sources poses a series of challenges that require specific optimization of the molecular photophysical properties. Here, we present a report on films of three different Eu3+ complexes characterized in terms of emission spectra and fluorescence decay. We compare molecular complexes in powder form and sublimed films, in films on glass and on a metal surface, and in films of thicknesses down to less than 3 nm (< 3 ML), approaching electrical coupling. Our photoluminescence experiments supported by scanning tunneling microscopy of sub-monolayers indicate that Eu3+(trensal) complexes are less affected by sublimation and more stable on the metal surface than typical beta diketonate complexes, making them promising candidates for electroluminescence devices.

cond-mat.mes-hall

Hybrid Quantum Systems: Coupling Single-Molecule Magnet Qudits with Industrial Silicon Spin Qubits

Molecular spin qudits offer an attractive platform for quantum memory, combining long coherence times with rich multi-level spin structures. Terbium bis(phthalocyaninato) (TbPc$_2$) exemplifies such systems, with demonstrated quantum control and chemical reproducibility. In hybrid quantum architectures, TbPc$_2$ can act as the primary memory element, with semiconductor qubits providing scalable readout and coupling. Here we present a step toward such a hybrid system: using an industrially manufactured silicon metal-oxide-semiconductor (SiMOS) spin qubit to detect electronic spin transitions of an ensemble of TbPc$_2$ molecules. The readout is based on a compact and robust protocol that applies a microwave pulse while all gate voltages defining the qubit are held at a fixed operating point. This protocol, which combines simultaneous Rapid adiabatic Passage and Spin- Selective tunneling (RPSS), enables high-contrast resonance detection and avoids repeated $\pi$-pulse recalibration common in decoupling schemes. By demonstrating ensemble detection, we establish a foundation for integrating molecular quantum memories with industrial qubit platforms and mark an important step toward single-molecule hybrid quantum technologies.

cond-mat.mes-hall

Optically detected nuclear magnetic resonance of coherent spins in a molecular complex

Nuclear magnetic resonance (NMR) is a powerful tool for applications ranging from chemical analysis to quantum information processing. Achieving optical initialization and detection of molecular nuclear spins promises new opportunities - including improved NMR signals at low magnetic field, sensitivity down to the single-molecule level, and full access to atomically precise molecular architectures for quantum technologies. In this study, we report optical readout of coherently controlled nuclear spins in a europium-based molecular crystal. By harnessing ultra-narrow optical transitions, we achieve optical initialization and detection of nuclear spin states. Through radio-frequency driving, we address two nuclear quadrupole resonances, characterized by narrow inhomogeneous linewidths and a distinct correlation with the optical transition frequency. We implement Rabi oscillations, spin echo and dynamical decoupling techniques, achieving nuclear spin quantum coherence with a lifetime of up to 2 ms. These results highlight the capabilities of optically detected NMR (ODNMR) and underscore the potential of molecular nuclear spins for quantum information processing.

quant-ph

Self-stabilized charge states in a double-decker molecular magnet on Pb(111)

Electron charging play key roles in physiochemical processes, whose intrinsic stabilization in single molecules is desirable for tailoring molecular functionality and developing molecular devices, but remains elusive on surfaces. Here, we show molecular charge states can be self-stabilized via intramolecular distortion in single bis(phthalocyaninato)terbium(III) (TbPc2) double-decker molecules, that were grown on Pb(111) substrate. Using scanning tunneling microscopy and spectroscopy, we identify fractions of TbPc2 molecules reduce to 2-fold symmetry, expressing energy-split molecular orbitals and two types of different spin states. Our first principles calculations unveil that the symmetry reduction is induced by charging-triggered Jahn-Teller distortions, which lifts the degenerate orbitals into two 2-fold symmetric orbitals. Single or double occupancy of the lower-energy orbital results in different molecular spin states. Such intramolecular distortion traps the excess electrons stably without explicit involvement of the substrate, in contrast to previously observed molecular charge states. These charged single molecule can be manipulated with the tip individually. This study offers a new avenue for tailoring the charge and spin states of molecules.

cond-mat.mes-hall

Nonlinearity of the Fidelity in Open Qudit Systems: Gate and Noise Dependence in High-dimensional Quantum Computing

High-dimensional quantum computing has generated significant interest due to its potential to address scalability and error correction challenges faced by traditional qubit-based systems. This paper investigates the Average Gate Fidelity (AGF) of single qudit systems under Markovian noise in the Lindblad formalism, extending previous work by developing a comprehensive theoretical framework for the calculation of higher-order correction terms. We derive general expressions for the perturbative expansion of the Average Gate Infidelity (AGI) in terms of the environmental coupling coefficient and validate these with extensive numerical simulations, emphasizing the transition from linear to nonlinear behaviour in the strong coupling regime. Our findings highlight the dependence of AGI on qudit dimensionality, quantum gate choice, and noise strength, providing critical insights for optimising quantum gate design and error correction protocols. Additionally, we utilise our framework to identify universal bounds for the AGI in the strong coupling regime and explore the practical implications for enhancing the performance of near-term qudit architectures. This study offers a robust foundation for future research and development in high-dimensional quantum computing, contributing to the advancement of robust, high-fidelity quantum operations.

quant-ph

Femtosecond spin-state switching dynamics of spin-crossover molecules condensed in thin films

The photoinduced switching of Fe(II)-based spin-crossover complexes from singlet to quintet takes place at ultrafast time scales. This a priori spin-forbidden transition triggered numerous time-resolved experiments of solvated samples to elucidate the mechanism at play. The involved intermediate states remain uncertain. We apply ultrafast x-ray spectroscopy in molecular films as a method sensitive to spin, electronic, and nuclear degrees of freedom. Combining the progress in molecule synthesis and film growth with the opportunities at x-ray free-electron lasers, we analyze the transient evolution of the Fe L3 fine structure at room temperature. Our measurements and calculations indicate the involvement of an Fe triplet intermediate state. The high-spin state saturates at half of the available molecules, limited by molecule-molecule interaction within the film.

cond-mat.mes-hall

Unconventional band structure via combined molecular orbital and lattice symmetries in a surface-confined metallated graphdiyne sheet

Graphyne (GY) and graphdiyne (GDY)-based materials represent an intriguing class of two-dimensional (2D) carbon-rich networks with tunable structures and properties surpassing those of graphene. However, the challenge of fabricating atomically well-defined crystalline GY/GDY-based systems largely hinders detailed electronic structure characterizations. Here, we report the emergence of an unconventional band structure in mesoscopically regular (~1 {\mu}m) metallated GDY sheets featuring a honeycomb lattice on Ag(111) substrates. Employing complementary scanning tunnelling and angle-resolved photoemission spectroscopies, electronic band formation with a gap of 2.5 eV is rigorously determined in agreement with real-space electronic characteristics. Extensive density functional theory calculations corroborate our observations as well as recent theoretical predictions that doubly degenerate frontier molecular orbitals on a honeycomb lattice give rise to flat, Dirac and Kagome bands close to Fermi level. These results illustrate the tremendous potential of engineering novel band structures via molecular orbital and lattice symmetries in atomically precise 2D carbon scaffolds.

cond-mat.mtrl-sci

Noisy Qudit vs Multiple Qubits : Conditions on Gate Efficiency for Enhancing Fidelity

Today, multiple new platforms are implementing qudits, $d$-level quantum bases of information, for Quantum Information Processing (QIP). It is therefore crucial to study their efficiencies for QIP compared to more traditional qubit platforms. We present a comparative study of the infidelity scalings of a qudit and $n$-qubit systems, both with identical Hilbert space dimensions and noisy environments. The first-order response of the Average Gate Infidelity (AGI) to the noise in the Lindblad formalism, which was found to be gate-independent, was calculated analytically in the two systems being compared. This yielded a critical curve $O(d^2/\log_2(d))$ of the ratio of their respective gate times in units of decoherence time. This quantity indicates how time-efficient operations on these systems are. The curve delineates regions where each system has a higher rate of increase of the AGI than the other. This condition on gate efficiency was applied to different existing platforms. It was found that specific qudit platforms possess gate efficiencies competitive with state-of-the-art qubit platforms. Numerical simulations complemented this work and allowed for discussion of the applicability and limits of the linear response formalism.

quant-ph

Rare-Earth Molecular Crystals with Ultra-narrow Optical Linewidths for Photonic Quantum Technologies

Rare-earth ions are promising solid state systems to build light-matter interfaces at the quantum level. This relies on their potential to show narrow optical homogeneous linewidths or, equivalently, long-lived optical quantum states. In this letter, we report on europium molecular crystals that exhibit linewidths in the 10s of kHz range, orders of magnitude narrower than other molecular centers. We harness this property to demonstrate efficient optical spin initialization, coherent storage of light using an atomic frequency comb, and optical control of ion-ion interactions towards implementation of quantum gates. These results illustrate the utility of rare-earth molecular crystals as a new platform for photonic quantum technologies that combines highly coherent emitters with the unmatched versatility in composition, structure, and integration capability of molecular materials.

physics.optics

Magnetic properties of transition metal dimers probed by inelastic neutron scattering

The physical characterisation and understanding of molecular magnetic materials is one of the most important steps towards the integration of such systems in hybrid spintronic devices. Amongst the many characterisation techniques employed in such a task, Inelastic Neutron Scattering (INS) stands as one of the most powerful and sensitive tools to investigate their spin dynamics. Herein, the magnetic properties and spin dynamics of two dinuclear complexes, namely [(M(hfacac)$_2$)$_2$(bpym)] (where M = Ni$^{2+}$, Co$^{2+}$, abbreviated in the following as Ni$_2$, Co$_2$) are reported. These are model systems that could constitute fundamental units of future spintronic devices. By exploiting the highly sensitive IN5 Cold INS spectrometer, we are able to gain a deep insight into the spin dynamics of Ni$_2$ and to fully obtain the microscopic spin Hamiltonian parameters; while for Co$_2$, a multitude of INS transitions are observed demonstrating the complexity of the magnetic properties of octahedral cobalt-based systems.

cond-mat.mes-hall

Molecule-based coherent light-spin interfaces for quantum information processing -- optical spin state polarization in a binuclear Europium complex

The success of the emerging field of solid-state optical quantum information processing (QIP) critically depends on the access to resonant optical materials. Rare-earth ions (REIs) are suitable candidates for QIP protocols due to their extraordinary photo-physical and magnetic quantum properties such as long optical and spin coherence lifetimes ($T_2$). However, molecules incorporating REIs, despite having advantageous properties such as atomically exact quantum tunability, inherent scalability, and large portability, have not yet been studied for QIP applications. As a first testimony of the usefulness of REI molecules for optical QIP applications, we demonstrate in this study that narrow spectral holes can be burned in the inhomogeneously broadened $^5$D$_0\to^7$F$_0$ optical transition of a binuclear Eu(III) complex, rendering a homogeneous linewidth ($\Gamma_h$) = 22 $\pm$ 1 MHz, which translates as $T_2 = 14.5$ $\pm$ 0.7 ns at 1.4 K. Moreover, long-lived spectral holes are observed, demonstrating efficient polarization of Eu(III) ground state nuclear spins, a fundamental requirement for all-optical spin initialization and addressing. These results elucidate the usefulness of REI-based molecular complexes as versatile coherent light-spin interfaces for applications in quantum communications and processing.

quant-ph

Observation of Cooperative Electronic Quantum Tunneling: Increasing Accessible Nuclear States in a Molecular Qudit

As an extension of two-level quantum bits (qubits), multilevel systems, so-called qudits, where d represents the Hilbert space dimension, have been predicted to reduce the number of iterations in quantum computation algorithms. This has been tested in the well-known [TbPc2]0 SMM, which allowed the implementation of the Grover algorithm in a single molecular unit. In the quest for molecular systems possessing an increased number of accessible nuclear spin states, we explore herein a dimeric Tb2-SMM via single crystal {\mu}-SQUID measurements at sub-Kelvin temperatures. We observe ferromagnetic interactions between the Tb(III) ions and cooperative quantum tunneling of the electronic spins with spin ground state \textit{J} = {\pm}6. The strong hyperfine coupling with the Tb(III) nuclear spins leads to a multitude of spin reversal paths leading to seven strong hyperfine driven tunneling steps in the hysteresis loops. Our results show the possibility to read-out the Tb(III) nuclear spin states via the cooperative tunneling of the electronic spins, making the dimeric Tb2-SMM an excellent nuclear spin qudit candidate with d =16.

quant-ph

Cyano-functionalized Ag-bis-acetylide wires on Ag(110)

Organometallic nanostructures are promising candidates for applications in optoelectronics, magnetism and catalysis. Our bottom-up approach employs a cyano-functionalized terminal alkyne species (CN-DETP) on the Ag(110) surface to fabricate 2D domains of regularly stacked Ag-acetylide nanowires. We unravel their adsorption properties and give evidence to their organometallic character with the aid of complementary surface-sensitive techniques, i.e. scanning tunneling microscopy, X-ray photoelectron spectroscopy and near-edge X-ray absorption fine-structure spectroscopy. Guided by the anisotropic (110) surface, highly oriented nanowires form in two enantiomorphic domains of regularly stacked trans isomers, whereby the bifunctional design of CN-DETP gives rise to orthogonal bonding motifs. Based on STM imaging, we find high thermal stability of the Ag-bis-acetylide wires, without conversion into graphdiyne chains. Our approach based on orthogonal bifunctionalization and selective functional group recognition extends the toolbox of creating alkyne-based nanostructures at interfaces.

physics.app-ph

Generalized Ramsey Interferometry Explored with a Single Nuclear Spin Qudit

Qudits, with their state space of dimension d > 2, open fascinating experimental prospects. The quantum properties of their states provide new potentialities for quantum information, quantum contextuality, expressions of geometric phases, facets of quantum entanglement and many other foundational aspects of the quantum world, which are unapproachable with qubits. We here experimentally investigate the quantum dynamics of a qudit (d = 4) that consists of a single 3/2 nuclear spin embedded in a molecular magnet transistor geometry, coherently driven by a microwave electric field. We propose and implement three protocols based on a generalization of the Ramsey interferometry to a multilevel system. First, the standard Ramsey interference is used to measure the accumulation of geometric phases. Then, two distinct transitions of the nuclear spin are addressed to measure the phase of an iSWAP quantum gate. Finally, through a succession of two Hadamard gates, the coherence time of a 3-state superposition is measured.

cond-mat.mes-hall

Spin-State dependent Conductance Switching in Single Molecule-Graphene Junctions

Spin-crossover (SCO) molecules are versatile magnetic switches with applications in molecular electronics and spintronics. Downscaling devices to the single-molecule level remains, however, a challenging task since the switching mechanism in bulk is mediated by cooperative intermolecular interactions. Here, we report on electron transport through individual Fe-SCO molecules coupled to few-layer graphene electrodes \textit{via} $\pi - \pi$ stacking. We observe a distinct bistability in the conductance of the molecule and a careful comparison with density functional theory (DFT) calculations allows to associate the bistability with a SCO-induced orbital reconfiguration of the molecule. We find long spin-state lifetimes that are caused by the specific coordination of the magnetic core and the absence of intermolecular interactions according to our calculations. In contrast with bulk samples, the SCO transition is not triggered by temperature but induced by small perturbations in the molecule at any temperature. We propose plausible mechanisms that could trigger the SCO at the single-molecule level.

cond-mat.mes-hall

On-Surface Structural and Electronic Properties of Spontaneously Formed Tb$_2$Pc$_3$ Single Molecule Magnets

The single molecule magnet (SMM) bis(phthalocyaninato)terbium (III) (TbPc$_2$) has attracted steady research attention as an exemplar system for realizing molecule-based spin electronics. In this paper, we report on the spontaneous formation of Tb$_2$Pc$_3$ species from TbPc$_2$ precursors via sublimation in ultrahigh vacuum (UHV) onto an Ag(111) surface. The molecules on the surface are inspected using combined scanning tunneling (STM) and non-contact atomic force microscopies (nc-AFM) at 5 Kelvin. Submolecular resolution and height dependent measurements supported by density functional theory (DFT) calculations unambiguously show the presence of both TbPc$_2$ and Tb$_2$Pc$_3$ species. The synthesis of Tb$_2$Pc$_3$ species under UHV conditions is independently confirmed by chemical analysis. The high-resolution AFM imaging allows us to register the orientation of the topmost Pc ligand in both Tb$_2$Pc$_3$ and TbPc$_2$ relative to the underlying Ag(111) surface. Measurements of the electronic structure reveal the selective appearance of a Kondo signature with temperature $\sim$ 30K in the Tb$_2$Pc$_3$ species, localized to the Pc ligand lobes. We attribute the presence of the Kondo resonance on select Tb$_2$Pc$_3$ molecules to the orientation of internal molecular ligands. High-resolution AFM imaging identifies geometric distortions between Tb$_2$Pc$_3$ molecules with and without the Kondo effect, the result of the complex interplay between structural and electronic differences.

cond-mat.mes-hall