Homonuclear Systems Research Articles

Heterobimetallic NiFe Complex for Photocatalytic CO2 Reduction: United Efforts of NiFe Dual Sites.

Catalytic CO2 reduction poses a significant challenge for the conversion of CO2 into chemicals and fuels. Ni-Fe carbon monoxide dehydrogenase ([NiFe]-CODH) effectively mediates the reversible conversion of CO2 and CO at a nearly thermodynamic equilibrium potential, highlighting the heterobimetallic cooperation for the design of CO2 reduction catalysts. However, numerous NiFe biomimetic model complexes have realized little success in CO2 reduction catalysis, which underscores the crucial role of precise bimetallic configuration and functionality. Herein, we presented a heterobimetallic NiFe complex for the photocatalytic reduction of CO2 to CO, demonstrating significantly enhanced catalytic performance compared to the homonuclear NiNi catalyst. Photocatalytic and mechanistic investigations revealed that with the assistance of a redox-active phenanthroline ligand, NiFe achieves dual-site activation of CO2 through a pivotal intermediate, NiII(μ-CO22--κC:κO)FeII, where the Lewis acidity of the FeII site plays an important role, as corroborated in the homonuclear FeFe system. This study introduces the first heteronuclear NiFe molecular catalyst capable of efficiently catalyzing the reduction of CO2 to CO, deepening insights into heterobimetallic cooperation and offering a novel strategy for designing highly active and selective CO2 reduction catalysts.

Ultracold charged atom-dimer collisions: State-selective charge exchange and three-body recombination

Based on an accurate determination of the potential energy surfaces of Rb3+ correlated to its first asymptotic limit Rb++Rb(5s)+Rb(5s), we identify the presence of intersections of a pair of singlet and triplet surfaces over all interparticle distances, leading to Jahn-Teller (JT) couplings. We elaborate scenarios for charge exchange between ultracold charged atom-dimer complex (Rb+Rb2+ or Rb++Rb2), predicting a strong selectivity on the preparation of the initial state of the dimer. We also demonstrate that the JT couplings must drive the three-body recombination (TBR) of Rb+, Rb, and Rb at ultracold energies. Using the current analysis, we provide a consistent picture of the TBR experiments performed in ion-atom hybrid Rb samples. We also demonstrate the presence of JT coupling as a general phenomenon in the singly charged homonuclear alkali triatomic systems. Published by the American Physical Society 2024

The re-entrant transition from the molecular to atomic phases of dense fluids: The case of hydrogen.

A simple phenomenological thermodynamic model is developed to describe the chemical bonding and unbonding in homonuclear diatomic systems. This model describes the entire phase diagram of dimer-forming systems and shows a transition from monomers to dimers, with monomers favored at both very low and very high pressures, as well as at high temperatures. In the context of hydrogen, the former region corresponds to hydrogen present in most interstellar gas clouds, while the latter is associated with the long sought-after fluid metallic phase. The model predicts a molecular to atomic fluid transition in dense deuterium, which is in agreement with recently reported experimental measurements.

Quantum exchange symmetry induces charge diffusion and trapping in ultracold gases

For a homonuclear ion-atom system, we show that the exchange symmetry leads to special outcomes for ion transport that manifest themselves in ultracold experiments. We compute the two body charge hopping probabilities and rates, which are used to model charge hopping in the dynamics of an ultracold 6/7 Li+ ion immersed within an ultracold gas of 6/7 Li atoms at micro-Kelvin temperatures. We show that the charge hopping and collisional diffusion compete, giving unique results leading to charge trapping in regions of high atomic density gradient. These investigations in ion-atom systems open a new approach to probe quantum phenomena in various systems with exchange symmetry.

Nuclear structure and Breit interaction effects in relativistic molecular electronic structure calculations

We examine the effects of nuclear structure and the self-consistent treatment of the Breit interaction on the calculation of properties associated with PT-odd interactions in TlF. We also demonstrate that 99.9999% of the Breit energy in TlF is recovered from the one-centre contributions to the interaction energy in the self-consistent field approximation. The formulation of our electronic structure code, BERTHA, facilitates the evaluation of all one-centre effects using efficient methods borrowed from relativistic atomic physics at negligible computational cost. A further analysis of this behaviour is provided for the homonuclear mean-field system, At, in the Dirac–Hartree–Fock–Breit approximation. For closed-shell systems, a formal analysis of the origin of this behaviour suggests that this computational economy may be of general applicability in relativistic molecular electronic structure theory.

Adiabatic Passage through Level Anticrossings in Systems of Chemically Inequivalent Protons Incorporating Parahydrogen: Theory, Experiment, and Prospective Applications.

Level anticrossings (LACs) are ubiquitous in quantum systems and have been exploited for spin-order transfer in hyperpolarized nuclear magnetic resonance spectroscopy. This paper examines the manifestations of adiabatic passage through a specific type of LAC found in homonuclear systems of chemically inequivalent coupled protons incorporating parahydrogen (pH2). Adiabatic passage through such a LAC is shown to elicit translation of the pH2 spin order. As an example, with prospective applications in biomedicine, proton spin polarizations of at least 19.8 ± 2.6% on the methylene protons and 68.7 ± 0.5% on the vinylic protons of selectively deuterated allyl pyruvate ester are demonstrated experimentally. After ultrasonic spray injection of a precursor solution containing propargyl pyruvate and a dissolved Rh catalyst into a chamber pressurized with 99% para-enriched H2, the products are collected and transported to a high magnetic field for NMR detection. The LAC-mediated hyperpolarization of the methylene protons is significant because of the stronger spin coupling to the pyruvate carbonyl 13C, setting up an ideal initial condition for subsequent coherence transfer by selective INEPT. Furthermore, the selective deuteration of the propargyl side arm increases the efficiency and polarization level. LAC-mediated translation of parahydrogen spin order completes the first step toward a new and highly efficient route for the 13C NMR signal enhancement of pyruvate via side-arm hydrogenation with parahydrogen.

Homonuclear J-coupling spectroscopy using J-synchronized echo detection

In the strong coupling regime with J-coupling much larger than chemical shift differences, J-coupling spectroscopy enables spectral identification of molecules even when conventional NMR fails. While this classically required the presence of a heteronucleus, we recently showed that J-coupling spectra can be acquired in many homonuclear systems using spin-lock induced crossing (SLIC). Here, we present an alternative method using a spin echo train in lieu of a spin-locking SLIC pulse, which has a number of advantages. In particular, spin echo acquisition within the pulse train enables simultaneous collection of time and frequency data. The resulting 2D spectrum can be used to study dynamic spin evolution, and the time domain data can be averaged to create a 1D J-coupling spectrum with increased signal-to-noise ratio.

Accurate calculations for the Dirac electron in the field of two-center Coulomb field: Application to heavy ions

The relativistic Dirac equation for a bound electron in the field of two fixed positive charges is revisited. In contrast to the one center case this three dimensional equation is separable only partially around the azimuthal angle φ, because of the commutation of the Dirac Hamiltonian only with the z component of the total angular momentum Jz. In this work we determine the variational exact solution of this two center problem using a basis constructed by linear combinations of relativistic Slater type spinor wave functions with non integer powers of the radii r1 and r2 on the two centers. We present in some detail the determination of the two center integrations involved. The solutions are obtained by a minimax procedure, that we have developed with a new iterative scheme. We use independent large and small components of the Dirac spinor. This permits us to take control of the spurious solutions, and gives us the possibility to avoid them by the appropriate choice of the wave function parameters. We investigate the behavior of the electron in its 1sσg level of the diatomic homo-nuclear systems A2(2Z-1)+, where A represents the heavy element and Z its atomic number. In the case of heavy ions we study the dependance of the electron energy on the internuclear distance, this gives us an indication for the conditions of atomic collapse, which can induce electron-positron pair production. Our approach has the advantage of needing small basis sets for a relative error of the of 10-7-10-8. It can also be extended easily to the excited level such as the 1sσu level.

Theory and simulations of homonuclear three-spin systems in rotating solids.

The homonuclear dipolar coupling is the internal spin interaction that contributes the most to the line shapes in magic-angle-spinning (MAS) 1H NMR spectra of solids, and linewidths typically extend over several hundred Hertz, limiting the 1H resolution. Understanding and reducing this contribution could provide rich structural information for organic solids. Here, we use average Hamiltonian theory to study two- and three-spin systems in the fast MAS regime. Specifically, we develop analytical expressions to third order in the case of two and three inequivalent spins (I = ½). The results show that the full third-order expression of the Hamiltonian, without secular approximations or truncation to second order, is the description that agrees the best, by far, with full numerical calculations. We determine the effect on the NMR spectrum of the different Hamiltonian terms, which are shown to produce both residual shifts and splittings in the three-spin systems. Both the shifts and splittings have a fairly complex dependence on the spinning rate with the eigenstates having a polynomial ωr dependence. The effect on powder line shapes is also shown, and we find that the anisotropic residual shift does not have zero average so that the powder line shape is broadened and shifted from the isotropic position. This suggests that in 1H MAS spectra, even at the fastest MAS rates attainable today, the positions observed are not exactly the isotropic shifts.

Accurate semiempirical potential energy curves for the a3Σ+-state of NaCs, KCs, and RbCs.

A five parameter semiempirical Tang-Toennies type model is used to describe the potential curves of the a3Σ+-state of the heteronuclear polar molecules NaCs, KCs, and RbCs. These molecules are of current interest in experiments at ultra-cold conditions to explore the effects of the strong dipole-dipole forces on the collective many-body quantum behavior. New quantum phenomena are also anticipated in systems consisting of atomic species with different fermion/boson statistics. The model parameters are obtained by simultaneously fitting all five of the parameters to the extensive LIF-Fourier transform spectroscopy published by Tiemann and collaborators [e.g., Docenko et al. J. Phys. B: At., Mol. Opt. Phys. 39, S929-S943 (2006)], who also report best fit potential curves. Although the new potentials are in good agreement with the earlier potentials, they have the advantage that they are continuous over the entire range of internuclear distances and have the correct long-range behavior. The scattering lengths for all isotope combinations show good agreement with dedicated experiments where available. The new potentials are also in excellent agreement with combining rules based on the potentials of the homonuclear systems.

A Portable NMR Spectrometer With a Probe Head Combining RF and DC Capabilities to Generate Pulsed-Field Gradients

Portable nuclear magnetic resonance (NMR) spectrometers are used in various scientific fields. A vast number of applications are suitable for low-field permanent magnets. However, most of these systems lack the ability of pulsed-field gradients as these require cumbersome additional hardware. We herein report an NMR probe head that incorporates a radio frequency (RF)-coil equipped with pulsed-field gradient capabilities in a single center-tapped solenoid. We developed a circuitry allowing for the application of direct currents without disturbing the RF reception capabilities. Furthermore, we present a System-on-Chip-based NMR spectrometer. Combined with the NMR probe head, it represents a versatile low-cost system capable of field gradient generation. The probe head is characterized in terms of scatter parameters, quality factor, and transversal field homogeneity. We exhibit simulation data of the field gradient and present the required external circuitry. Experimental results show further the dephasing capabilities of the gradient and give insights into the spatial shape. Finally, the system is applied for the mapping of J-couplings in 1-butanol via zero-quantum coherences. A theoretical analysis of the pulse sequence is given for a homonuclear two-spin system. The experimental results demonstrate the potential use of this setup.

Resonant transmission of weakly bound multi-atomic molecules

This article examines resonant tunnelling of multi-atomic systems, extending the body of work on resonant tunnelling in this area beyond diatomic homo-nuclear systems. We consider diatomic molecules with distinct atoms having different masses, and linear triatomic molecules with indistinguishable atoms. The molecule is incident in the bound state upon a step potential with an energy increase of V0 for each atom. We calculate the probabilities of reflection pR and transmission pT in the bound state and the dependence on the energy of the molecule. We find that, as was the case for the homo-nuclear molecule, resonant transmission for diatomic molecules with distinguishable atoms occurs for arbitrarily weak binding, and pT is close to one for finite binding energy. We also find resonant transmission for linear triatomic molecules. We show results for the time-dependent Schrödinger equation which agree with resonant transmission. We also consider the transmission of an N-atom one-dimensional molecule.

Controllable hybrid shape of correlation and squeezing

Two- and three-mode correlation and squeezing of spontaneous parametric four-wave mixing (SPFWM) and fourth-order fluorescence (FL) composite signals are investigated theoretically and experimentally in both homonuclear (two-level) and heteronuclearlike (V-type level) molecular systems of $\mathrm{P}{\mathrm{r}}^{3+}$:YSO. By selecting different time positions, changing the power, and changing the frequency detuning of the laser field, the competition between the composite signals is demonstrated. It is found that as the laser parameters change, the signal evolves from a nonlinear ${\ensuremath{\chi}}^{(4)}$ process resulting in a FL signal to a SPFWM signal $({\ensuremath{\chi}}^{(3)}$ process). In addition, the competition effect between the signals determines the evolution of the shape of the correlation from a pure sharp to a two-stage (mixed) shape and finally to a pure broad peak amplitude. Furthermore, the signal evolution determines the magnitude of squeezing, which can control the noise level. Such progress may find potential applications in optical hybrid communication and information processing.

Metastable homonuclear diatomic trications [formula omitted] for elements X from the first three rows of the periodic table

Motivated by a systematic stability scan of the homonuclear diatomic systems with elements from hydrogen to argon, we investigated in detail the ensuing five candidates for metastable trications, viz., O23+, P23+, S23+, Cl23+, and Ar23+ by multireference configuration interaction computations. Each of these tricationic systems exhibits a barrier in its ground state potential energy curve leading to quasi-bound nuclear motion. The resulting lifetimes vary drastically; while S23+ and Cl23+ in their lowest vibrational states can be regarded as practically stable, the predicted lifetimes of O23+ and Ar23+ are too short to allow a mass spectroscopic detection of these systems by current experimental capabilities. In the case of Ar23+, the theoretically predicted existence of quasibound vibrational levels also depends on whether or not relativistic corrections are taken into account.

Heteronuclear Efimov resonances in ultracold quantum gases

Abstract The Efimov scenario is a universal three-body effect addressing many areas of modern quantum physics. It plays an important role in the transition between few- and many-body physics and has enabled important breakthroughs in the understanding of the universal few-body theory. We review the basic concepts of the Efimov scenario with specific emphasis on the similarities and differences between homonuclear and heteronuclear systems. In the latter scenario, the existence of a second, independently tunable interaction parameter enables novel few-body phenomena that are universal and have no counterexamples in the homonuclear case. We discuss recent experimental approaches using ultracold atomic gases with magnetically tunable interactions and elucidate the role of short-range interactions in the emergence of universal and non-universal behavior.

Longitudinal relaxation in dipole-coupled homonuclear three-spin systems: Distinct correlations and odd spectral densities.

A system of three dipole-coupled spins exhibits a surprisingly intricate relaxation behavior. Following Hubbard's pioneering 1958 study, many authors have investigated different aspects of this problem. Nevertheless, on revisiting this classic relaxation problem, we obtain several new results, some of which are at variance with conventional wisdom. Most notably from a fundamental point of view, we find that the odd-valued spectral density function influences longitudinal relaxation. We also show that the effective longitudinal relaxation rate for a non-isochronous three-spin system can exhibit an unusual inverted dispersion step. To clarify these and other issues, we present a comprehensive theoretical treatment of longitudinal relaxation in a three-spin system of arbitrary geometry and with arbitrary rotational dynamics. By using the Liouville-space formulation of Bloch-Wangsness-Redfield theory and a basis of irreducible spherical tensor operators, we show that the number of relaxation components in the different cases can be deduced from symmetry arguments. For the isochronous case, we present the relaxation matrix in analytical form, whereas, for the non-isochronous case, we employ a computationally efficient approach based on the stochastic Liouville equation.

Molecular alignment effect on the photoassociation process via a pump-dump scheme.

The photoassociation processes via the pump-dump scheme for the heternuclear (Na + H → NaH) and the homonuclear (Na + Na → Na2) molecular systems are studied, respectively, using the time-dependent quantum wavepacket method. For both systems, the initial atom pair in the continuum of the ground electronic state (X(1)Σ(+)) is associated into the molecule in the bound states of the excited state (A(1)Σ(+)) by the pump pulse. Then driven by a time-delayed dumping pulse, the prepared excited-state molecule can be transferred to the bound states of the ground electronic state. It is found that the pump process can induce a superposition of the rovibrational levels |v, j〉 on the excited state, which can lead to the field-free alignment of the excited-state molecule. The molecular alignment can affect the dumping process by varying the effective coupling intensity between the two electronic states or by varying the population transfer pathways. As a result, the final population transferred to the bound states of the ground electronic state varies periodically with the delay time of the dumping pulse.

Alternative analytical forms to model diatomic systems based on the deformed exponential function.

Using a deformed exponential function and the molecular-orbital theory for the simplest molecular ion, two new analytical functions are proposed to represent the potential energy of ground-state diatomic systems. The quality of these new forms was tested by fitting the ab initio electronic energies of the system LiH, LiNa, NaH, RbH, KH, H2, Li2, K2, H 2 (+) , BeH(+) and Li 2 (+) . From these fits, it was verified that these new proposals are able to adequately describe homonuclear, heteronuclear and cationic diatomic systems with good accuracy. Vibrational spectroscopic constant results obtained from these two proposals are in good agreement with experimental data.

Zero-range-potential model for strong-field molecular processes: Dynamic polarizability and photodetachment cross section

We develop a general theoretical framework for the analytical description of the interaction of a model diatomic molecular system with an intense, arbitrarily polarized monochromatic laser field. The model molecule comprises an electron in the field of two zero-range potentials separated by the internuclear distance. This model has an exact analytical solution within the theoretical framework of the quasistationary quasienergy (Floquet) approach. In addition to the development of this general framework, we also present a detailed analysis of the weak-field limit, within which we obtain both the frequency-dependent polarizability and the angle-resolved photodetachment cross section for the model system. These fundamental properties are analyzed for both homonuclear and heteronuclear molecular systems in a linearly polarized laser field, for both ground and excited electronic states, and for arbitrary orientation of the molecular axis relative to the polarization vector of the laser field. The analytical expressions for the polarizability and angle-resolved photoelectron spectra exhibit characteristic double-slit interference patterns, allowing one to study their dependence on the parameters of the problem beyond the level of the Born approximation.

Minimum-Time Control of Local Quantum Gates for Two-Qubit Homonuclear Systems

This paper presents a design method for minimum-time control of homonuclear spin systems. We firstly estimate the minimum time based on a multiple time-scale analysis, following which an improved gradient algorithm is deigned to search the control profile. Numerical simulations show that this method can effectively reduce the search efforts for finding the minimum-time control for two-spin systems.