Heteronuclear Systems Research Articles

Upconversion Luminescence in a Photostable Ion‐Paired Yb−Eu Heteronuclear Complex

AbstractLanthanide‐based upconversion molecular complexes have potential application in diverse fields and attracted considerable research interest in recent years. However, the similar coordination reactivity of lanthanide ions has constrained the designability of target molecule with well‐defined structure, and many attempts obtained statistical mixtures. Herein, an ion‐paired Yb−Eu heteronuclear complex [Eu(TpPy)2][Yb(ND)4] (TpPy=tris[3‐(2‐pyridyl)pyrazolyl]hydroborate, ND=3‐cyano‐2‐methyl‐1,5‐naphthyridin‐4‐olate) was designed and synthesized. Thanks to the radius difference between Eu3+ (1.07 Å) and Yb3+ (0.98 Å) ions, the hexadentate TpPy ligand was selected to coordinate with Eu3+ and the Yb3+ with a smaller radius was chelated by bidentate ND ligand. As a result, the sites of Eu3+ and Yb3+ in the complex can be clarified by high‐resolution mass spectrometry and single‐crystal structure analysis. Upon the excitation of Yb3+ at 980 nm, the upconversion emission of Eu3+ was realized through a cooperative sensitization process. Furthermore, [Eu(TpPy)2][Yb(ND)4] demonstrated excellent photostability during continuous high‐power density 980 nm laser irradiation, with a LT95 (the time to 95 % of the initial emission intensity) of 420 minutes. This work provides the first example of a pure ion‐paired Yb−Eu heteronuclear complex upconversion system and may bring insights into rational design of lanthanide‐based upconversion molecular complexes.

Upconversion Luminescence in a Photostable Ion-Paired Yb-Eu Heteronuclear Complex.

Lanthanide-based upconversion molecular complexes have potential application in diverse fields and attracted considerable research interest in recent years. However, the similar coordination reactivity of lanthanide ions has constrained the designability of target molecule with well-defined structure, and many attempts obtained statistical mixtures. Herein, an ion-paired Yb-Eu heteronuclear complex [Eu(TpPy)2][Yb(ND)4] (TpPy = tris[3-(2-pyridyl)pyrazolyl]hydroborate, ND = 3-cyano-2-methyl-1,5-naphthyridin-4-olate) was designed and synthesized. Thanks to the radius difference between Eu3+ (1.07 Å) and Yb3+ (0.98 Å) ions, the hexadentate TpPy ligand was selected to coordinate with Eu3+ and the Yb3+ with a smaller radius was chelated by bidentate ND ligand. As a result, the sites of Eu3+ and Yb3+ in the complex can be clarified by high-resolution mass spectrometry and single-crystal structure analysis. Upon the excitation of Yb3+ at 980 nm, the upconversion emission of Eu3+ was realized through a cooperative sensitization process. Furthermore, [Eu(TpPy)2][Yb(ND)4] demonstrated excellent photostability during continuous high-power density 980 nm laser irradiation, with a LT95 (the time to 95% of the initial emission intensity) of 420 minutes. This work provides the first example of a pure ion-paired Yb-Eu heteronuclear complex upconversion system and may bring insights into rational design of lanthanide-based upconversion molecular complexes.

Structural and Photophysical Trends in Rhenium(I) Carbonyl Complexes with 2,2':6',2″-Terpyridines.

This is the first comprehensive review of rhenium(I) carbonyl complexes with 2,2':6',2″-terpyridine-based ligands (R-terpy)-encompassing their synthesis, molecular features, photophysical behavior, and potential applications. Particular attention has been devoted to demonstrating how the coordination mode of 2,2':6',2″-terpyridine (terpy-κ2N and terpy-κ3N), structural modifications of terpy framework (R), and the nature of ancillary ligands (X-mono-negative anion, L-neutral ligand) may tune the photophysical behavior of Re(I) complexes [Re(X/L)(CO)3(R-terpy-κ2N)]0/+ and [Re(X/L)(CO)2(R-terpy-κ3N)]0/+. Our discussion also includes homo- and heteronuclear multicomponent systems with {Re(CO)3(R-terpy-κ2N)} and {Re(CO)2(R-terpy-κ3N)} motifs. The presented structure-property relationships are of high importance for controlling the photoinduced processes in these systems and making further progress in the development of more efficient Re-based luminophores, photosensitizers, and photocatalysts for modern technologies.

A Single‐Scan Ultraselective Heteronuclear Polarization Transfer Method for Unambiguous Complex Structure Assignment

AbstractComplex nuclear magnetic resonance (NMR) signals of organic compounds containing multiple analogous substructures or mixtures pose a significant challenge to structural identification, thus resulting in frequent misassignment of structures. The GEMSTONE method, a single‐scan technique that selectively excites a specific proton signal among the crowded NMR signals, was recently proposed as a solution. However, its extension to the polarization transfer method for heteronuclear spin systems was unsuccessful. Herein, we present an extension method that addresses the altered heteronuclear polarization transfer efficiency and enables the acquisition of ultraselective 13C and 1H‐13C correlation NMR subspectra with hertz‐level signal selectivity in both dimensions. We demonstrate the effectiveness of this technique in the structural analysis of a chromopeptide pharmaceutical and a diastereomeric mixture of a fungicide.

A Single-Scan Ultraselective Heteronuclear Polarization Transfer Method for Unambiguous Complex Structure Assignment.

Complex nuclear magnetic resonance (NMR) signals of organic compounds containing multiple analogous substructures or mixtures pose a significant challenge to structural identification, thus resulting in frequent misassignment of structures. The GEMSTONE method, a single-scan technique that selectively excites a specific proton signal among the crowded NMR signals, was recently proposed as a solution. However, its extension to the polarization transfer method for heteronuclear spin systems was unsuccessful. Here, we present an extension method that addresses the altered heteronuclear polarization transfer efficiency and enables the acquisition of ultraselective 13C and 1H-13C correlation NMR subspectra with hertz-level signal selectivity in both dimensions. We demonstrate the effectiveness of this technique in the structural analysis of a chromopeptide pharmaceutical and a diastereomeric mixture fungicide.

Fascinating Electrocatalysts with Dispersed Di-Metals in MN3 -M'N4 Moiety as Two Active Sites Separately for N2 and CO2 Reduction Reactions and Jointly for CN Coupling and Urea Production.

The idealized urea electrocatalyst is crucial to boost the CN coupling reaction and simultaneously suppress their isolated reduction process after adsorbing N2 and CO2 molecules. Therefore, the dispersed MN3 -M'N4 moiety is investigated systematically, including 26 homonuclear and 650 heteronuclear di-metal systems. After, 205 stable systems are selected using lowest-energy principle and ab initio molecular dynamics simulations. According to three possible pathways, NCON, CO, and OCOH to produce urea, a five-step high-throughput screening method for excellent catalytic activity and a five-aspect high-throughput screening strategy for outstanding catalytic selectivity are proposed, respectively. The potential determined steps and the limiting potential through three pathways are identified. The data indicates both CO pathway and OCOH pathway are more competitive at lower Gibbs free energy. Significantly, the most favorite RuN3 -CoN4 combination possesses an extremely low limiting potential of -0.80V for urea production, meanwhile it exists a strong foundation for experimental preparation. This work not only broadens electrocatalytic potentiality of developing di-metals as two active sites, but also provides a feasible high-throughput screening recipe for urea production.

Geometric potential of the exact electron factorization: Meaning, significance, and application

The theoretical and computational description of materials properties is a task of utmost scientific and technological importance. A first-principles description of electron-electron interactions poses an immense challenge that is usually approached by converting the many-electron problem to an effective one-electron problem. There are different ways to obtain an exact one-electron theory for a many-electron system. An emergent method is the exact electron factorization (EEF) -- one of the branches of the exact factorization approach to many-body systems. In the EEF, the Schr\"odinger equation for one electron, in the environment of all other electrons, is formulated. The influence of the environment is reflected in the potential ${v}^{\mathrm{H}}$, which represents the energy of the environment, and in a potential ${v}^{\mathrm{G}}$, which has a geometrical meaning. In this paper, we focus on ${v}^{\mathrm{G}}$ and study its properties in detail. We investigate the geometric origin of ${v}^{\mathrm{G}}$ as a metric measuring the change of the environment, exemplify how translation and scaling of the state of the environment are reflected in ${v}^{\mathrm{G}}$, and explain its shape for homo- and heteronuclear diatomic model systems. Based on the close connection between the EEF and density functional theory, we also use ${v}^{\mathrm{G}}$ to provide an alternative interpretation to the Pauli potential in orbital-free density functional theory.

Asymmetric Coupled Dual‐Atom Sites for Selective Photoreduction of Carbon Dioxide to Acetic Acid

AbstractPhotocatalytic reduction of CO2 to value‐added liquid fuels is a promising approach to alleviate the global energy and environmental problems. However, highly selective production of C2+ products from CO2 reduction reaction (CO2RR) is very difficult because of the sluggish CC coupling reaction. An asymmetric coupled heteronuclear photocatalyst is designed to overcome this limitation. The new catalyst contains single atoms of nickel and cobalt loaded on titanium dioxide. It exhibits an impressive 71% selectivity for acetic acid. The experimental data and theoretical calculations reveal that the Ni and Co single atom sites not only significantly lower the energy barrier of electron transfer in photocatalysis but also efficiently promote the CC coupling toward CH3COOH. The high activity of such a heteronuclear catalyst system will shed light on the future development of effective materials for CO2RR.

Extending NMR Quantum Computation Systems by Employing Compounds with Several Heavy Metals as Qubits

Nuclear magnetic resonance (NMR) is a spectroscopic method that can be applied to several areas. Currently, this technique is also being used as an experimental quantum simulator, where nuclear spins are employed as quantum bits or qubits. The present work is devoted to studying heavy metal complexes as possible candidates to act as qubit molecules. Nuclei such 113Cd, 199Hg, 125Te, and 77Se assembled with the most common employed nuclei in NMR-QIP implementations (1H, 13C, 19F, 29Si, and 31P) could potentially be used in heteronuclear systems for NMR-QIP implementations. Hence, aiming to contribute to the development of future scalable heteronuclear spin systems, we specially designed four complexes, based on the auspicious qubit systems proposed in our previous work, which will be explored by quantum chemical calculations of their NMR parameters and proposed as suitable qubit molecules. Chemical shifts and spin–spin coupling constants in four complexes were examined using the spin–orbit zeroth-order regular approximation (ZORA) at the density functional theory (DFT) level, as well as the relaxation parameters (T1 and T2). Examining the required spectral properties of NMR-QIP, all the designed complexes were found to be promising candidates for qubit molecules.

Hamiltonian tomography by the quantum quench protocol with random noise

In this article, we introduce a framework for Hamiltonian tomography of multi-qubit systems with random noise. We adopt the quantum quench protocol to reconstruct a many-body Hamiltonian by local measurements that are distorted by random unitary operators and time uncertainty. In particular, we consider a transverse field Ising Hamiltonians describing interactions of two spins $1/2$ and three-qubit Hamiltonians of a heteronuclear system within the radio-frequency field. For a sample of random Hamiltonians, we report the fidelity of reconstruction versus the amount of noise quantified by two parameters. Furthermore, we discuss the correlation between the accuracy of Hamiltonian tomography and the number of pairs of quantum states involved in the framework. The results provide valuable insight into the robustness of the protocol against random noise.

Dinitrogen Activation and Functionalization by Heteronuclear Metal Cluster Anions FeV2C2- at Room Temperature.

It is of great importance to study the mechanisms to activate dinitrogen (N2), the very inert molecule, under mild conditions. Gas-phase metal clusters are being actively generated to react with N2 to identify new reaction types and mechanisms. Herein, an unprecedented, mechanistically unique metal atom (Fe or V) ejection in the thermal reaction of FeV2C2- with N2 has been identified using mass spectrometry, photoelectron imaging spectroscopy, and quantum chemistry calculations. Strong evidence suggests that the complete cleavage of the N≡N triple bond and subsequent functionalization of two N atoms via C-N coupling were achieved in this reaction. The complementary cooperation between V atoms with strong electron-donating ability and an Fe atom with large electron-withdrawing ability as well as the geometric flexibility of the Fe-V-V ring drives the whole reaction. The important role of C ligands in N≡N cleavage was also revealed. This study emphasizes the importance of heteronuclear metal systems for N2 fixation.

Surprising absence of strong homonuclear coupling at low magnetic field explored by two-field nuclear magnetic resonance spectroscopy.

Strong coupling of nuclear spins, which is achieved when their scalar coupling is greater than or comparable to the difference in their Larmor precession frequencies in an external magnetic field, gives rise to efficient coherent longitudinal polarization transfer. The strong coupling regime can be achieved when the external magnetic field is sufficiently low, as is reduced proportional to the field strength. In the present work, however, we demonstrate that in heteronuclear spin systems these simple arguments may not hold, since heteronuclear spin-spin interactions alter the value. The experimental method that we use is two-field nuclear magnetic resonance (NMR), exploiting sample shuttling between the high field, at which NMR spectra are acquired, and the low field, where strong couplings are expected and at which NMR pulses can be applied to affect the spin dynamics. By using this technique, we generate zero-quantum spin coherences by means of a nonadiabatic passage through a level anticrossing and study their evolution at the low field. Such zero-quantum coherences mediate the polarization transfer under strong coupling conditions. Experiments performed with a -labeled amino acid clearly show that the coherent polarization transfer at the low field is pronounced in the spin subsystem under proton decoupling. However, in the absence of proton decoupling, polarization transfer by coherent processes is dramatically reduced, demonstrating that heteronuclear spin-spin interactions suppress the strong coupling regime, even when the external field is low. A theoretical model is presented, which can model the reported experimental results.

Parametrically excited star-shaped patterns at the interface of binary Bose-Einstein condensates

A Faraday-wave-like parametric instability is investigated via mean-field and Floquet analysis in immiscible binary Bose-Einstein condensates. The condensates form a so-called ball-shell structure in a two-dimensional harmonic trap. To trigger the dynamics, the scattering length of the core condensate is periodically modulated in time. We reveal that in the dynamics the interface becomes unstable towards the formation of oscillating patterns. The interface oscillates subharmonically, exhibiting an $m$-fold rotational symmetry that can be controlled by maneuvering the amplitude and the frequency of the modulation. Using Floquet analysis we are able to predict the generated interfacial tension of the mixture and derive a dispersion relation for the natural frequencies of the emergent patterns. A heteronuclear system composed of $^{87}\mathrm{Rb}\ensuremath{-}^{85}\mathrm{Rb}$ atoms can be used for the experimental realization of the phenomenon, yet our results are independent of the specifics of the employed atomic species and of the parameters such as scattering lengths and trap strengths at which the driving is applied.

Design of a Graphene Nitrene Two-Dimensional Catalyst Heterostructure Providing a Well-Defined Site Accommodating One to Three Metals, with Application to CO2 Reduction Electrocatalysis for the Two-Metal Case.

Recently, the reduction of CO2 to fuels has been the subject of numerous studies, but the selectivity and activity remain inadequate. Progress has been made on single-site two-dimensional catalysts based on graphene coupled to a metal and nitrogen for the CO2 reduction reaction (CO2RR); however, the product is usually CO, and the metal-N environment remains ambiguous. We report a novel two-dimensional graphene nitrene heterostructure (grafiN6) providing well-defined active sites (N6) that can bind one to three metals for the CO2RR. We find that homobimetallic FeFe-grafiN6 could reduce CO2 to CH4 at -0.61 V and to CH3CH2OH at -0.68 V versus reversible hydrogen electrode, with high product selectivity. Moreover, the heteronuclear FeCu-grafiN6 system may be significantly less affected by hydrogen evolution reaction, while maintaining a low limiting potential (-0.68 V) for C1 and C2 mechanisms. Binding metals to one N6 site but not the other could promote efficient electron transport facilitating some reaction steps. This framework for single or multiple metal sites might also provide unique catalytic sites for other catalytic processes.

Time optimal control based on classification of quantum gates

We study the minimum time to implement an arbitrary two-qubit gate in two heteronuclear spins systems. We give a systematic characterization of two-qubit gates based on the invariants of local equivalence. The quantum gates are classified into four classes, and for each class the analytical formula of the minimum time to implement the quantum gates is explicitly presented. For given quantum gates, by calculating the corresponding invariants one easily obtains the classes to which the quantum gates belong. In particular, we analyze the effect of global phases on the minimum time to implement the gate. Our results present complete solutions to the optimal time problem in implementing an arbitrary two-qubit gate in two heteronuclear spins systems. Detailed examples are given to typical two-qubit gates with or without global phases.

Preparation of a heteronuclear two-atom system in the three-dimensional ground state in an optical tweezer

We report the realization of a heteronuclear two-atom of $^{87}$Rb-$^{85}$Rb in the ground state of an optical tweezer (OT). Starting by trapping two different isotopic single atoms, a $^{87}$Rb and a $^{85}$Rb in two strongly focused and linearly polarized OT with 4 $\mu$m apart, we perform simultaneously three dimensional Raman sideband cooling for both atoms and the obtained 3D ground state probabilities of $^{87}$Rb and $^{85}$Rb are 0.91(5) and 0.91(10) respectively. There is no obvious crosstalk observed during the cooling process. We then merge them into one tweezer via a species-dependent transport, where the species-dependent potentials are made by changing the polarization of the OTs for each species from linear polarization to the desired circular polarization. The measurable increment of vibrational quantum due to merging is $0.013(1)$ for the axial dimension. This two-atom system can be used to investigate cold collisional physics, to form quantum logic gates, and to build a single heteronuclear molecule. It can also be scaled up to few-atom regime and extended to other atomic species and molecules, and thus to ultracold chemistry.

Universal three-body parameter of heavy-heavy-light systems with a negative intraspecies scattering length

The Three-Body Parameter(3BP) $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-}$ is crucial to understanding Efimov physics, and a universal 3BP has been shown in experiments and theory in ultracold homonuclear gases. The 3BP of heteronuclear systems was predicted to possess much richer properties than the homonuclear counterparts for the large parameter space. In this work, we investigate the universal properties of $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-}$ for the Heavy-Heavy-Light(HHL) system with negative intraspecies scattering length $a_{\scriptscriptstyle HH}$. We find that $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-}$ follows a universal behavior determined by the van der Waals(vdW) interaction and the mass ratio. An analytic formula of $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-}$ is given as a function of $a_{\scriptscriptstyle HH}$, which allows an intuitive understanding of how does $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-}$ depend on the mass ratio and the vdW length $r_{\scriptscriptstyle vdW}$. In a special case, when the two heavy atoms are in resonance, $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-}$ is approximately a constant: $a^{\scriptscriptstyle(1)}_{\scriptscriptstyle-} = -(6.3\pm0.6)\, r_{\scriptscriptstyle vdW,HL}$.

Observation of resonant scattering between ultracold heteronuclear Feshbach molecules

We report the observation of a dimer-dimer inelastic collision resonance for ultracold Feshbach molecules made of bosonic sodium and rubidium atoms. This resonance, which we attribute to the crossing of the dimer-dimer threshold with a heteronuclear tetramer state, manifests itself as a pronounced inelastic loss peak of dimers when the interspecies scattering length between the constituent atoms is tuned. Near this resonance, a strong modification of the temperature dependence of the dimer-dimer scattering is observed. Our result provides insight into the heteronuclear four-body system consisting of heavy and light bosons and offers the possibility of investigating ultracold molecules with tunable interactions.

Correlated Gaussian approach to anisotropic resonantly interacting few-body systems

Quantum mechanical few-body systems in reduced dimensionalities can exhibit many interesting properties such as scale-invariance and universality. Analytical descriptions are often available for integer dimensionality, however, numerical approaches are necessary for addressing dimensional transitions. The Fully-Correlated Gaussian method provides a variational description of the few-body real-space wavefunction. By placing the particles in a harmonic trap, the system can be described at various degrees of anisotropy by squeezing the confinement. Through this approach, configurations of two and three identical bosons as well as heteronuclear (Cs–Cs–Li and K–K–Rb) systems are described during a continuous deformation from three to one dimension. We find that the changes in binding energies between integer dimensional cases exhibit a universal behavior akin to that seen in avoided crossings or Zeldovich rearrangement.

Two-photon photoassociation spectroscopy of the Σ+2 YbLi molecular ground state

We report on measurements of the binding energies of several weakly bound vibrational states of the paramagnetic $^{174}$Yb$^{6}$Li molecule in the electronic ground state using two-photon spectroscopy in an ultracold atomic mixture confined in an optical dipole trap. We theoretically analyze the experimental spectrum to obtain an accurate description of the long-range potential of the ground state molecule. Based on the measured binding energies, we arrive at an improved value of the interspecies $s$-wave scattering length $a_{s0}=30$ $a_0$. Employing coherent two-photon spectroscopy we also observe the creation of ''dark'' atom-molecule superposition states in the heteronuclear Yb-Li system. This work is an important step towards the efficient production of ultracold YbLi molecules via association from an ultracold atomic mixture.