Heteronuclear Systems Research Articles

Ultracold magnetically tunable interactions without radiative-charge-transfer losses betweenCa+, Sr+, Ba+, andYb+ions and Cr atoms

The Ca$^+$, Sr$^+$, Ba$^+$, and Yb$^+$ ions immersed in an ultracold gas of the Cr atoms are proposed as experimentally feasible heteronuclear systems in which ion-atom interactions at ultralow temperatures can be controlled with magnetically tunable Feshbach resonances without charge transfer and radiative losses. \textit{Ab initio} techniques are applied to investigate electronic-ground-state properties of the (CaCr)$^+$, (SrCr)$^+$, (BaCr)$^+$, and (YbCr)$^+$ molecular ions. The potential energy curves, permanent electric dipole moments, and static electric dipole polarizabilities are computed. The spin restricted open-shell coupled cluster method restricted to single, double, and noniterative triple excitations, RCCSD(T), and the multireference configuration interaction method restricted to single and double excitations, MRCISD, are employed. The scalar relativistic effects are included within the small-core energy-consistent pseudopotentials. The leading long-range induction and dispersion interaction coefficients are also reported. Finally, magnetic Feshbach resonances between the Ca$^+$, Sr$^+$, Ba$^+$, and Yb$^+$ ions interacting with the Cr atoms are analyzed. The present proposal opens the way towards robust quantum simulations and computations with ultracold ion-atom systems free of radiative charge transfer losses.

Methodology for solid state NMR off-resonance study of molecular dynamics in heteronuclear systems

Methodology for the study of dynamics in heteronuclear systems in the laboratory frame was described in the previous paper [1]. Now the methodology for the study of molecular dynamics in the solid state heteronuclear systems in the rotating frame is presented. The solid state NMR off-resonance experiments were carried out on a homemade pulse spectrometer operating at the frequency of 30.2MHz for protons. This spectrometer includes a specially designed probe which contains two independently tuned and electrically isolated coils installed in the coaxial position on the dewar. A unique probe design allows working at three slightly differing frequencies off and on resonance for protons and at the frequency of 28.411MHz for fluorine nuclei with complete absence of their electrical interference. The probe allows simultaneously creating rf magnetic fields at off-resonance frequencies within the range of 30.2–30.6MHz and at the frequency of 28.411MHz. Presented heteronuclear cross-relaxation off-resonance experiments in the rotating frame provide information about molecular dynamics.

Interaction-induced decay of a heteronuclear two-atom system.

Two-atom systems in small traps are of fundamental interest for understanding the role of interactions in degenerate cold gases and for the creation of quantum gates in quantum information processing with single-atom traps. One of the key quantities is the inelastic relaxation (decay) time when one of the atoms or both are in a higher hyperfine state. Here we measure this quantity in a heteronuclear system of 87Rb and 85Rb in a micro optical trap and demonstrate experimentally and theoretically the presence of both fast and slow relaxation processes, depending on the choice of the initial hyperfine states. This experimental method allows us to single out a particular relaxation process thus provides an extremely clean platform for collisional physics studies. Our results have also implications for engineering of quantum states via controlled collisions and creation of two-qubit quantum gates.

Regulation of charge delocalization in a heteronuclear Fe2 ru system by a stepwise photochromic process.

Heteronuclear complexes FeCp2 -DTE-C≡C-Ru(dppe)2 Cl (1 o; dppe=1,2-bis(diphenylphosphino)ethane, Cp=cyclopentadienyl, DTE=dithienylethene) and FeCp2-DTE-C≡C-Ru(dppe)2-C≡C-DTE-FeCp2 (2 oo), with redox-active ferrocenyl and ruthenium centers separated by a photochromic DTE moiety, were prepared to achieve photoswitchable charge delocalization and Fe⋅⋅⋅Ru electronic communication. Upon UV-light irradiation of 2 oo, the Fe⋅⋅⋅Ru heterometallic electronic interaction is increasingly facilitated with stepwise photocyclization, 2 oo→2 co→2 cc; this is ascribed to the gradual increase in π-conjugated systems. The near-infrared absorptions in mixed-valence species [2 oo](+) /[2 co](+) /[2 cc](+) are gradually intensified following the conversion of [2 oo](+) →[2 co](+) →[2 cc](+) , which demonstrates that the extent of charge delocalization shows progressive enhancement with stepwise photocyclization. As revealed by electrochemical, spectroscopic, and theoretical studies, complex 2 exhibits nine switchable states through stepwise photochromic and reversible redox processes.

Dual emission tunable in the near-infrared (NIR) and visible (VIS) spectral range by mix-LnMOF.

In this study, we describe the synthetic approach, crystallographic structure, luminescent behavior and elucidation of the channels of the energy conversion in heteronuclear coordination polymers with emission in the visible (Eu(3+) and organic ligand) and near-infrared (Nd(3+)) range. The [(Nd0.9Eu0.1)2(dipc)3(H2O)3]n·nH2O, [(Nd0.7Eu0.3)2(dipc)3(H2O)3]n·nH2O, [(Nd0.5Eu0.5)2(dipc)3(H2O)3]n·nH2O, [(Nd0.3Eu0.7)2(dipc)3(H2O)3]n·nH2O, [(Nd0.1Eu0.9)2(dipc)3(H2O)3]n·nH2O, [Eu2(dipc)3(H2O)3]n·nH2O and [Nd2(dipc)3(H2O)3]n·nH2O materials are obtained by hydrothermal conditions from pyridine-2,6-dicarboxylic acid (H2dipc) and Ln2O3 oxide (Ln = Eu and Nd). The fine structures in the emission spectrum and spectral profile are used to investigate the ion responsible for the emission characteristics of a material (6), based on coordination polyhedron. The heteronuclear systems show emission in the dual spectral range (NIR-VIS) tuned for blue or red. The tuning of emission on the red (Eu(3+)) or blue (organic ligand) range may be performed by controlling the stoichiometric ratio of the lanthanide ions and by controlling the excitation wavelength. Nd(3+) ions display self-absorption of emission to dipc ligand, resulting in interference on the emission band profile ranging from 400 to 600 nm. The energetic process of energy transfer is operated by a cascade of energy transfer, from dipc ligand mainly to Eu(3+) ions and finishing on the Nd(3+) ion. The efficient sensitization to Nd(3+) by Eu(3+) ions is due to the presence of many resonant energy levels and the short distance between these ions.

Prediction of a weakly bound excited state of Efimov character in aLi7He24system

We carry out calculations on the van der Waals trimer (LiHe2)-Li-7-He-4 using the mapping method within the frame of hyperspherical coordinates, which allows us to give accurate binding energies and wave functions for both the ground and excited state of the system. When the realistic two-body potentials are adopted, the system presents an excited state which shows Efimov character. We study the range of the interaction strength in which the excited state could exist and find that the state persists within the experiment error band for binding energy of LiHe molecule. We also study the three-body parameter (3BP) of (LiHe2)-Li-7-He-4 system and its relationship with the background scattering length alpha(HeHe). Our calculations demonstrate that the 3BP of (LiHe2)-Li-7-He-4 system is dependent on the value of the scattering length aHeHe, independent of the short-range details of the He-He interaction. The results confirm the prediction of Wang et al. [Phys. Rev. Lett. 109, 243201 (2012)] that the 3BP for a heteronuclear atomic system is universally determined from the van der Waals lengths and the homonuclear scattering length.

α-Fluoro Phosphonocarboxylates: the NMR Analysis of the Heteronuclear ABMX Spin System

The α-fluorophosphonocarboxylate analogs of bisphosphonates have recently received attention due to their activity against Rab geranylgeranyl transferase, an enzyme implicated in a number of disease conditions. Most of the NMR data reported in the literature describing dialkyl α-fluorophosphonates are defined as first-order spectra. Here, we report a second-order pattern observed in 19F NMR spectrum, being a part of heteronuclear ABMX spin system. Such a spin system, CH2C(F)P, was subjected to NMR analysis supported by iteration.

Multichannel quantum-defect theory for magnetic Feshbach resonances in heteronuclear group-I systems

We present a multichannel quantum-defect theory for magnetic Feshbach resonances in the interaction of two heteronuclear group I atoms. The theory provides a unified and a uniform description of resonances in all partial waves, and enables the characterization of large number of resonances in terms of very few parameters. For the sample system of $^6$Li$^{40}$K, we present descriptions of all resonances in $aa$, $ab$, and $ba$ channels, in partial waves $s$ ($l=0$) through $h$ ($l=5$), and in a magnetic field of 0 through 1000 Gauss. All resonances, including those in nonzero partial waves, are fully characterized using the newly developed parametrization of Gao [Phy. Rev. A \textbf{84}, 022706 (2011)].

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.

Time optimal quantum control of two-qubit systems

We study the optimal quantum control of heteronuclear two-qubit systems described by a Hamiltonian containing both nonlocal internal drift and local control terms. We derive an explicit formula to compute the minimum time required to steer the system from an initial state to a specified final state. As applications the minimal time to implement Controlled-NOT gate, SWAP gate and Controlled-U gate is calculated in detail. The experimental realizations of these quantum gates are explicitly presented.

Systematic Theoretical Study of Non-nuclear Electron Density Maxima in Some Diatomic Molecules

First, exploratory calculations were performed to investigate the presence of non-nuclear maxima (NNMs) in ground-state electron densities of homonuclear diatomic molecules from hydrogen up to calcium at their equilibrium geometries. In a second stage, only for the cases in which these features were previously detected, a rigorous analysis was carried out by several combinations of theoretical methods and basis sets in order to ensure that they are not only calculation artifacts. Our best results support that Li2, B2, C2, and P2 are molecules that possess true NNMs. A NNM was found in values obtained from the largest basis sets for Na2, but it disappeared at the experimental geometry because optimized bond lengths are significantly inaccurate for this case (deviations of 0.10 Å). Two of these maxima are also observed in Si2 with CCSD and large basis sets, but they are no longer detected as core-valence correlation or multiconfigurational wave functions are taken into account. Therefore, the NNMs in Si2 can be considered unphysical features due to an incomplete treatment of electron correlation. Finally, we show that a NNM is encountered in LiNa, representing the first discovery of such electron density maxima in a heteronuclear diatomic system at its equilibrium geometry, to our knowledge. Some results for LiNa, found in variations in internuclear distances, suggest that molecular electric moments, such as dipole and quadrupole, are sensitive to the presence of NNMs.

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.

Ultrashort-laser-pulse-mediated asymmetry in the branching of dissociated fragments of HD+: Effects of a weak third pulse and carrier envelope phase of the dissociating pulse

We have numerically explored the possibility of controlling the branching ratio of the two distinguishable photodissociation products of HD${}^{+}$ (neutral D and neutral H) in an ultrashort laser field. In our multipulse scheme, a bound vibrational wave packet is generated in the ground electronic state of HD${}^{+}$ by vertical ionization from the ground state of HD. The control pulse acts on this wave packet at different time delays after the wave-packet generation is completed. It was found that, for a broad range of delay times between the pump pulse and the control pulse, any possible asymmetry in the branching ratio disappears due to the nonadiabatic coupling effects present in HD${}^{+}$. A third pulse, termed the driving pulse, with a relatively longer duration and a much weaker field strength, is introduced to counterbalance the nonadiabatic effects relevant for this heteronuclear system and to guide the dissociative reaction to a specific product channel. In fact, we have shown that the application of the driving pulse reproduces the branching-ratio pattern obtained on variation in the interpulse delay time between the pump pulse and the control pulse in the absence of the nonadiabatic coupling effects. The role of both the delay time between the pump pulse and the control pulse as well as the carrier envelope phase effects of the optical field of the control laser on the branching ratios in the two reaction channels were studied. The robustness of the driving pulse mediated asymmetry control, and any possible introduction of asymmetry by the driving pulse itself were also investigated.

Methodology for solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems

This work presents the theoretical analysis of cross-relaxation and its applications to the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. The solid state NMR experiments were carried out on a homemade pulse spectrometer operating at the frequency of 30.2MHz and 28.411MHz for protons and fluorines, respectively. It is worth noting that this spectrometer includes a specially designed probe which simultaneously works at two slightly differing frequencies for protons and fluorine nuclei with complete absence of their interference. Contrary to a large number of previous cross-relaxation studies [1–5], in our experiments proton spins can be polarized in the magnetic field B0 or excited by rf pulses, while fluorine spins are continuously saturated for a long time. The saturation of fluorines is maintained throughout the whole duration of the experiment. It leads to a simplification of the mathematical analysis of the experimental results.

Amplified x-ray emission from core-ionized diatomic molecules.

We predict high-gain x-ray lasing in molecular nitrogen by ultrafast core ionization with an x-ray free-electron laser source. To estimate the spectral and temporal output of this molecular x-ray laser, we solve generalized Maxwell-Bloch equations, keeping track of the electronic and nuclear degrees of freedom. The spectrum of the amplified x-ray emission shows a strong dependence on the gain-length product. Whereas the emission at small gain length is similar to the relatively broad x-ray fluorescence band, the spectrum is determined by a single frequency in the linear gain region. The vibrational wave packet dynamics during the x-ray emission process is examined. By preparation of the initial vibrational quantum state, the x-ray emission frequency can be tuned within the fluorescence band. The present scheme is applicable to other homo- and heteronuclear diatomic systems, thereby extending the spectral range of coherent x-ray radiation sources based on amplification on bound transitions.

How to Tickle Spins with a Fourier Transform NMR Spectrometer

In the long bygone days of continuous-wave nuclear magnetic resonance (NMR) spectroscopy, a selected transition within a multiplet of a high-resolution spectrum could be irradiated by a highly selective continuous-wave (CW) radio-frequency (rf) field with a very weak amplitude ω(2)/(2π)≤J. This causes splittings of connected transitions, allowing one to map the connectivities of all transitions within the energy-level diagram of the spin system. Such "tickling" experiments stimulated the invention of two-dimensional spectroscopy, but seem to have been forgotten for nearly 50 years. We show that tickling can readily be achieved in homonuclear systems with Fourier transform spectrometers by applying short pulses in the intervals between the sampling points. Extensions to heteronuclear systems are even more straightforward since they can be carried out using very weak CW rf fields.

Universal Three-Body Parameter in Heteronuclear Atomic Systems

In Efimov physics, a three-body parameter (3BP), previously regarded as nonuniversal, uniquely defines bound and scattering properties of three particles. A universal 3BP, however, has been recently shown in experiments and theory in ultracold homonuclear gases. Our present study further predicts a universal 3BP for heteronuclear atomic systems near broad Feshbach resonances and provides physical interpretations for its origin. We show that for a system composed of two light and one heavy atom, the physical origin of the universal 3BP is similar to the homonuclear case, while for systems composed by one light and two heavy atoms, the universality of the 3BP is now mostly controlled by the heavy-heavy interatomic properties. This new universality is explained by the universal properties of the van der Waals interactions in a simple Born-Oppenheimer picture. Finally, we show the numerically determined 3BPs for some combinations of alkali atoms used in ultracold experiments.

Refocused continuous-wave decoupling: A new approach to heteronuclear dipolar decoupling in solid-state NMR spectroscopy

A novel strategy for heteronuclear dipolar decoupling in magic-angle spinning solid-state nuclear magnetic resonance (NMR) spectroscopy is presented, which eliminates residual static high-order terms in the effective Hamiltonian originating from interactions between oscillating dipolar and anisotropic shielding tensors. The method, called refocused continuous-wave (rCW) decoupling, is systematically established by interleaving continuous wave decoupling with appropriately inserted rotor-synchronized high-power π refocusing pulses of alternating phases. The effect of the refocusing pulses in eliminating residual effects from dipolar coupling in heteronuclear spin systems is rationalized by effective Hamiltonian calculations to third order. In some variants the π pulse refocusing is supplemented by insertion of rotor-synchronized π/2 purging pulses to further reduce the residual dipolar coupling effects. Five different rCW decoupling sequences are presented and their performance is compared to state-of-the-art decoupling methods. The rCW decoupling sequences benefit from extreme broadbandedness, tolerance towards rf inhomogeneity, and improved potential for decoupling at relatively low average rf field strengths. In numerical simulations, the rCW schemes clearly reveal superior characteristics relative to the best decoupling schemes presented so far, which we to some extent also are capable of demonstrating experimentally. A major advantage of the rCW decoupling methods is that they are easy to set up and optimize experimentally.

Vibrational-rotational behavior of diatomic heteronuclear molecular systems in intense laser pulses

The dynamics of diatomic heteronuclear molecules in the low-frequency intense laser pulses is studied by numerical solution of the time-dependent Schrodinger equation and both rotational and vibrational degrees of freedom are taken into account. The interference stabilization against the dissociation process is found to take place in a strong field and is shown to result in trapping of population in different rotational-vibrational bound states due to efficient Raman V- and Λ-type transitions. The interplay between the vibrational and rotational dynamics of a molecule is investigated. The dissociation suppression due to the interference mechanism and all its attributes are established in the case of multiphoton coupling between the initial state and dissociation continuum.

Unexpected effects of third-order cross-terms in heteronuclear spin systems under simultaneous radio-frequency irradiation and magic-angle spinning NMR

We recently noted [R. K. Harris, P. Hodgkinson, V. Zorin, J.-N. Dumez, B. Elena, L. Emsley, E. Salager, and R. Stein, Magn. Reson. Chem. 48, S103 (2010)] anomalous shifts in apparent (1)H chemical shifts in experiments using (1)H homonuclear decoupling sequences to acquire high-resolution (1)H NMR spectra for organic solids under magic-angle spinning (MAS). Analogous effects were also observed in numerical simulations of model (13)C,(1)H spin systems under homonuclear decoupling and involving large (13)C,(1)H dipolar couplings. While the heteronuclear coupling is generally assumed to be efficiently suppressed by sample spinning at the magic angle, we show that under conditions typically used in solid-state NMR, there is a significant third-order cross-term from this coupling under the conditions of simultaneous MAS and homonuclear decoupling for spins directly bonded to (1)H. This term, which is of the order of 100 Hz under typical conditions, explains the anomalous behaviour observed on both (1)H and (13)C spins, including the fast dephasing observed in (13)C{(1)H} heteronuclear spin-echo experiments under (1)H homonuclear decoupling. Strategies for minimising the impact of this effect are also discussed.