Photoassociation Spectroscopy Research Articles

Analyzing the photoassociation spectrum of ultracold 85Rb 133Cs molecule in (3)3Σ+ state.

We establish a theoretical model to analyze the photoassociative spectroscopy of 85Rb 133Cs molecules in the (3)3Σ+ state. The vibrational energy, spin-spin coupling constant, and hyperfine interaction constant of the (3)3Σ+ state are determined based on nine observed vibrational levels. Consequently, the Rydberg-Klein-Rees potential energy curve of the (3)3Σ+ state is obtained and compared with the ab initial potential energy curve. Our model can be adopted to analyze the photoassociative spectroscopy of other heteronuclear alkali-metal diatomic molecules in the (3)3Σ+ state.

Potential energy curve for B1Π state of 85Rb133Cs obtained via genetic algorithm

We adopt the genetic algorithm to fit the potential energy curve for B1Π state of 85Rb133Cs molecule based on the data of rovibrational energy levels, which were observed previously by Fourier-transform spectroscopy and photoassociation spectroscopy. We explore the effect of different hyperparameter settings on the evolutionary process and final results to optimise the performance of the algorithm. Finally, the fitting procedure can reproduce the rovibrational levels with an error less than 0.06 cm−1 compared to the experimental data.

Electronic Structure, Spectroscopy, Cold Ion–Atom Elastic Collision Properties, and Photoassociation Formation Prediction of the (MgCs)+ Molecular Ion

In this paper, we extensively study the electronic structure, interactions, and dynamics of the (MgCs)+ molecular ion. The exchanges between the alkaline atom and the low-energy cationic alkaline earths, which are important in the field of cold and ultracold quantum chemistry, are studied. We use an ab initio approach based on the formalism of non-empirical pseudo-potential for Mg2+ and Cs+ cores, large Gaussian basis sets, and full-valence configuration interaction. In this context, the (MgCs)+ cation is treated as an effective two-electron system. Adiabatic potential energy curves and their spectroscopic constants for the ground and the first 20 excited states of 1,3Σ+ symmetries are determined. Furthermore, we identify the avoided crossings between the electronic states of 1,3Σ+ symmetries. These crossings are related to the charge transfer process between the two ionic limits, Mg/Cs+ and Mg+/Cs. Therefore, vibrational-level spacings and the transition and permanent dipole moments are presented and analyzed. Using the produced potential energy data, the ground-state scattering wave functions and elastic cross-sections are calculated for a wide range of energies. In addition, we predict the formation of a translationally and rotationally cold molecular ion (MgCs)+ in the ground-state electronic potential energy through a stimulated Raman-type process aided by ion–atom cold collision. In the low-energy limit (<1 mK), elastic scattering cross-sections exhibit Wigner law threshold behavior, while in the high-energy limit, the cross-sections act as a function of energy E go as E−1/3. A qualitative discussion about the possibilities of forming cold (MgCs)+ molecular ions by photoassociative spectroscopy is presented.

Analytic approximations to the strengths of near-threshold optical Feshbach resonances

Optical Feshbach resonances allow one to control cold atomic scattering, produce ultracold molecules, and study atomic interactions via photoassociation spectroscopy. In the limit of ultracold $s$-wave collisions, the strength of an optical Feshbach resonance can be expressed via an energy-independent parameter called the optical length. Here we give fully analytic approximate expressions for its magnitude applicable to near-threshold bound states of an excited molecular state dominated by a single resonant-dipole or van der Waals interaction. We express these magnitudes in terms of intuitive quantities, such as the laser intensity, the excited-state binding energy, the $s$-wave scattering length, and the Condon point. Additionally, we extend the utility of the optical length to associative stimulated Raman adiabatic passage in three-dimensional optical lattices by showing that the free-bound Rabi frequency induced by a laser coupling a pair of atoms in an optical lattice site can be approximately related to the trap frequency and the optical length.

Preparation of ultra-cold (36D<sub>5/2</sub>+ 6S<sub>1/2</sub>) Rydberg molecule and measurement of its permanent electric dipole moment

<sec>Ultra-cold long-range Rydberg molecules, consisting of a Rydberg atom and a ground-state atom or another Rydberg atom or ion, have attracted considerable attention due to their exaggerated properties, such as huge size, long chemical bond, large polarization and electric dipole moment, abundant vibrational states and exotic adiabatic potentials. The binding mechanism of Rydberg molecules is a low-energy scattering interaction between the Rydberg electron and the ground state atom for ground-Rydberg molecules or long-range multipole interaction for Rydberg-atom macrodimers and Rydberg-ion molecules, in contrast to covalent bonds, ionic bonds of normal and van der Waals interaction. Owing to its huge size, the dynamic evolution becomes slow compared with normal diatomic molecules and the ultra-long chemical bonds allow being imaged directly by high resolution imaging technology, which makes it convenient to observe the molecular dynamics process chemical reaction process in real time. The investigation of Rydberg molecules will be significant for understanding the mechanism of molecular collision and quantum chemical reaction.</sec><sec>In this work, we study the ultra-cold Rydberg-ground state molecules theoretically and experimentally. Theoretically, we calculate the adiabatic potential energy curve of cesium (36D<sub>5/2</sub>+ 6S<sub>1/2</sub>) Rydberg molecule based on the Fermi model of low energy electron scattering by numerically solving the Hamiltonian of Rydberg molecules. And also, we obtain its characteristic parameters, such as the potential depth, binding energy and equilibrium nuclear distance of Rydberg molecule. Experimentally, the Rydberg-ground molecules are investigated by a photoassociation spectroscopy, where two laser pulses are used to achieve a two-photon transition, and their spectra are obtained by ion detection technology. We successfully observe the Rydberg-ground state molecular spectra that correspond to a scattering triplet and a scattering single-triplet mixture (<sup>S,T</sup>Σ). The measured binding energy of Rydberg-ground state molecules is in good agreement with the theoretical result. In addition, taking the Rydberg-ground state molecules formed by scattering triplet (<sup>T</sup>Σ) for example, we demonstrate the spectrum broadening of Rydberg molecules in a weak electric field, from which we obtain the permanent electric dipole moments <inline-formula><tex-math id="M2">\begin{document}$|\bar{d}|$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221865_M2.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221865_M2.png"/></alternatives></inline-formula> of polar Rydberg-ground state molecules about (12.10<inline-formula><tex-math id="M3">\begin{document}$ \pm $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221865_M3.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221865_M3.png"/></alternatives></inline-formula>1.65) Debye ((4.76<inline-formula><tex-math id="M4">\begin{document}$ \pm $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221865_M4.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221865_M4.png"/></alternatives></inline-formula>0.65) <i>ea</i><sub>0</sub>). The results are consistent with the theoretical calculations. Our study provides a feasible scheme for the experimental preparation of D-type Rydberg-ground molecules, which is of great significance in studying the binding mechanism and the spectral characteristics of polar Rydberg molecules.</sec>

Resolving rotationally excited states of ultralong-range Rydberg molecules

We report experimental observations of the rotational structure in photoassociative spectroscopy of ultralong-range Rydberg molecules (ULRRMs) in an ultracold gas of $^{86}\mathrm{Sr}$. ULRRM spectroscopy probes scattering wave functions at much larger internuclear separations than photoassociative spectroscopy of low-lying electronic states. At such separations photon recoil momentum can lead to the transfer of significant angular momentum to the Rydberg molecule, evidence of which is provided through the distribution of excited rotational states. The visibility of the rotational structure is enhanced because, for collisions between ground-state $^{86}\mathrm{Sr}$ atoms, the large, near-resonant s-wave scattering length approaches the size of the ULRRM. Similar enhancement is not seen for $^{84}\mathrm{Sr}$, which has a much smaller scattering length. Results are interpreted with the aid of a theory that accounts for the recoil momentum associated with photoexcitation and the large $s$-wave scattering length in the entrance channel. While the observed rotational splittings and the qualitative trends in the relative intensities of the spectral features are well described by theory, the effects of recoil momentum are more prominent in the measured data than in the theory.

Observation of photoassociation spectroscopy of 23Na spinor Bose-Einstein condensate.

We report the high-resolution photoassociation (PA) spectroscopy of 23Na excited from the spin-1 Bose-Einstein Condensate (BEC) to the molecular state of 0g-(P3/2)v = 4 and 1g(P3/2)v = 91. By comparing the PA spectra of different spin configurations, we experimentally studied the effect of spin on the PA spectra. The experimental spectra comply well with the theoretical consideration. The results will play an important role in the study of the spin interaction and control of the antiferromagnetism in Na.

Reexamination of the ground-state Born-Oppenheimer Yb2 potential

The precision of the photoassociation spectroscopy of Yb dimer in degenerate gases is enough to improve the constraints on the new short-range gravity-like forces if the theoretical knowledge of the Born-Oppenheimer interatomic potential and non-Born-Oppenheimer interactions is refined [M. Borkowski et al. Sci. Rep. A {\bf 9}, 14807 (2019)]. The ground-state interaction potential of ytterbium dimer is investigated at the eXact 2-component core-correlated CCSD(T) level of {\it ab initio} theory in the complete basis set limit with extensive augmentation by diffuse functions. For the small basis set the comparison is made with the four-component relativistic finite-nuclei CCSD(T) calculations to identify the contraction of the dimer bond length as the main unrecoverable consequence of the scalar-relativistic approximation. Empirical constraint on the number of bound vibrational energy levels of the $^{174}$Yb$_2$ dimer is accounted for by representing the global {\it ab initio}-based Born-Oppenheimer potential with the model semianalytical function containing the scale and shift parameters. The results support the previous evaluation of the Yb dimer potentials from the photoassociation spectroscopy data and provide an accurate and flexible reference for future refinement of the constraints on the short-range gravity-like forces by ultracold atomic spectroscopy.

Heteronuclear Long-Range Rydberg Molecules.

We present the formation of homonuclear Cs_{2}, K_{2}, and heteronuclear CsK long-range Rydberg molecules in a dual-species magneto-optical trap for ^{39}K and ^{133}Cs by one-photon UV photoassociation. The different ground-state-density dependence of homo- and heteronuclear photoassociation rates and the detection of stable molecular ions resulting from autoionization provide an unambiguous assignment. We perform bound-bound millimeter-wave spectroscopy of long-range Rydberg molecules to access molecular states not accessible by one-photon photoassociation. Calculations based on the most recent theoretical model and atomic parameters do not reproduce the full set of data from homo- and heteronuclear long-range Rydberg molecules consistently. This shows that photoassociation and millimeter-wave spectroscopy of heteronuclear long-range Rydberg molecules provide a benchmark for the development of theoretical models.

Observation of Cesium (nD 5/2+6S 1/2) Ultralong-Range Rydberg-Ground MoleculesSupported by the National Key R&D Program of China (Grant No. 2017YFA0304203), the National Natural Science Foundation of China (Grant Nos. 11434007, 61835007, 61675123, 61775124, and 11904215), Changjiang Scholars and Innovative Research Team in Universities of Ministry of Education of China (Grant No. IRT 17R70), and the 1331 Project.

Ultralong-range Cs2 Rydberg-ground molecules (nD 5/2 + 6S 1/2 F) (33 ≤ n ≤ 39, F = 3 or 4) are investigated by a two-photon photo-association spectroscopy of an ultracold Cs gas. Two vibrational ground molecular spectra of triplet 3 Σ and hyperfine mixed singlet-triplet 1,3 Σ molecular states and their corresponding binding energies are attained. The experimental observations are simulated by an effective Hamiltonian including low energy electron scattering pseudopotentials, the spin-orbit interaction of the Rydberg atom, and the hyperfine interaction of the ground-state atom. The zero-energy singlet and triplet s-wave scattering lengths are extracted by comparing the experimental observations and calculations. Dependences of the measured binding energies on the effective principal quantum number, n eff = n − δD (δD is the quantum defect of Rydberg D state), yield the scaling of , for deep triplet potential and , for shallow mixed singlet-triplet potential well. The simulations of low-energy Rydberg electron scattering show agreement well with the experimental measurements.

Photoassociation spectroscopy of weakly bound Rb287 molecules near the 5P1/2+5S1/2 threshold by optical Bragg scattering in Bose-Einstein condensates

We report the high resolution photoassociation (PA) spectroscopy of a $^{87}Rb$ Bose-Einstein condensate (BEC) to excited molecular states near the dissociation limit of $5P_{1/2} +5S_{1/2}$ by optical Bragg scattering. Since the detection of optical Bragg scattering in BEC has a high signal-noise ratio, we obtain the high resolution PA spectrum of excited molecular states in the range of $\pm1$ GHz near the dissociation limit of $5P_{1/2} +5S_{1/2}$. We compare the results with the conventional method of trap loss and show that the results agree each other very well. Many interesting phenomena of excited molecular states are observed, such as light-induced frequency shift and the anomalous strong bound molecular lines at the atomic transition from $|F=1\rangle$ to $|F^{\prime}=2\rangle$. The observed excited molecular states in the range of $\pm1$ GHz near the dissociation limit of $5P_{1/2} +5S_{1/2}$ are never reported before, which will help to further improve the long range bound state models near the dissociation limit.

Cesium nDJ+6S1/2 Rydberg molecules and their permanent electric dipole moments

Cs$_2$ Rydberg-ground molecules consisting of a Rydberg, $nD_{J}$ (33 $\leq$ $n$ $\leq$ 39), and a ground state atom, 6$S_{1/2} (F=$3 or 4$)$, are investigated by photo-association spectroscopy in a cold atomic gas. We observe vibrational spectra that correspond to triplet $^T\Sigma$ and mixed $^{S,T}\Sigma$ molecular states. We establish scaling laws for the energies of the lowest vibrational states vs principal quantum number and obtain zero-energy singlet and triplet $s$-wave scattering lengths from experimental data and a Fermi model. Line broadening in electric fields reveals the permanent molecular electric-dipole moments; measured values agree well with calculations. We discuss the negative polarity of the dipole moments, which differs from previously reported cases.

Light-induced frequency shifts for the lowest vibrational levels of ultracold Cs2 in the molecular pure long-range $$0_g^-$$ state

The light-induced frequency shift (LIFS) of ultracold molecular ro-vibrational levels originates from the strong coupling of the atomic-scattering state and the bound-molecular state. In this paper, we present our experimental determination of the LIFSs of the lowest vibrational levels (ν = 0, 1) in the purely long-range $$0_g^-$$ state of ultracold cesium molecules. A high-resolution double photoassociation spectroscopy is developed, which serves as frequency ruler to measure the frequency shifts of the lowest molecular levels for Cs2. The experimental results are qualitatively consistent with the theoretical expectations.

Observation of spin-orbit-dependent electron scattering using long-range Rydberg molecules

We present experimental evidence for spin-orbit interaction of an electron as it scatters from a neutral atom. The scattering process takes place within a Rb$_2$ ultralong-range Rydberg molecule, consisting of a Rydberg atomic core, a Rydberg electron, and a ground state atom. The spin-orbit interaction leads to characteristic level splittings of vibrational molecular lines which we directly observe via photoassociation spectroscopy. We benefit from the fact that molecular states dominated by resonant $p$-wave interaction are particularly sensitive to the spin-orbit interaction. Our work paves the way for studying novel spin dynamics in ultralong-range Rydberg molecules. Furthermore, it shows that the molecular setup can serve as a microlaboratory to perform precise scattering experiments in the low-energy regime of a few meV.

A pathway to ultracold bosonic 23Na39K ground state molecules

We spectroscopically investigate a pathway for the conversion of 23Na39K Feshbach molecules into rovibronic ground state molecules via stimulated Raman adiabatic passage. Using photoassociation spectroscopy from the diatomic scattering threshold in the a3Σ+ potential, we locate the resonantly mixed electronically excited intermediate states and which, due to their singlet–triplet admixture, serve as an ideal bridge between predominantly a3Σ+ Feshbach molecules and pure X1Σ+ ground state molecules. We investigate their hyperfine structure and present a simple model to determine the singlet–triplet coupling of these states. Using Autler–Townes spectroscopy, we locate the rovibronic ground state of the 23Na39K molecule () and the second rotationally excited state N = 2 to unambiguously identify the ground state. We also extract the effective transition dipole moment from the excited to the ground state. Our investigations result in a fully characterized scheme for the creation of ultracold bosonic 23Na39K ground state molecules.

Weakly bound molecules as sensors of new gravitylike forces

Several extensions to the Standard Model of particle physics, including light dark matter candidates and unification theories predict deviations from Newton’s law of gravitation. For macroscopic distances, the inverse-square law of gravitation is well confirmed by astrophysical observations and laboratory experiments. At micrometer and shorter length scales, however, even the state-of-the-art constraints on deviations from gravitational interaction, whether provided by neutron scattering or precise measurements of forces between macroscopic bodies, are currently many orders of magnitude larger than gravity itself. Here we show that precision spectroscopy of weakly bound molecules can be used to constrain non-Newtonian interactions between atoms. A proof-of-principle demonstration using recent data from photoassociation spectroscopy of weakly bound Yb2 molecules yields constraints on these new interactions that are already close to state-of-the-art neutron scattering experiments. At the same time, with the development of the recently proposed optical molecular clocks, the neutron scattering constraints could be surpassed by at least two orders of magnitude.

Magnetic Feshbach resonances in ultracold collisions between Cs and Yb atoms

We investigate magnetically tunable Feshbach resonances in ultracold collisions between ground-state Yb and Cs atoms, using coupled-channel calculations based on an interaction potential recently determined from photoassociation spectroscopy. We predict resonance positions and widths for all stable isotopes of Yb, together with resonance decay parameters where appropriate. The resonance patterns are richer and more complicated for fermionic Yb than for spin-zero isotopes, because there are additional level splittings and couplings due to scalar and tensorial Yb hyperfine interactions. We examine collisions involving Cs atoms in a variety of hyperfine states, and identify resonances that appear most promising for experimental observation and for magnetoassociation to form ultracold CsYb molecules.

High-intensity two-frequency photoassociation spectroscopy of a weakly bound molecular state: Theory and experiment

We investigate two-frequency photoassociation of a weakly bound molecular state, focusing on a regime where the ac Stark shift is comparable to the halo-state energy. In this "high-intensity" regime, we observe features absent in low-intensity two-frequency photoassociation. We experimentally measure the spectra of $^{86}$Sr atoms coupled to the least bound state of the $^{86}$Sr$_2$ ground electronic channel through an intermediate electronically excited molecular state. We compare the spectra to a simple three-level model that includes a two-frequency drive on each leg of the transition. With numerical solution of the time-dependent Schrodinger equation, we show that this model accurately captures (1) the existence of experimentally observed satellite peaks that arise from nonlinear processes, (2) the locations of the two-photon peak in the spectrum, including ac Stark shifts, and (3) in some cases, spectral lineshapes. To better understand these numerical results, we develop an approximate treatment of this model, based on Floquet and perturbation theory, that gives simple formulas that accurately capture the halo-state energies. We expect these expressions to be valuable tools to analyze and guide future two-frequency photoassociation experiments.

Two-photon photoassociation spectroscopy of CsYb: Ground-state interaction potential and interspecies scattering lengths

We perform two-photon photoassociation spectroscopy of the heteronuclear CsYb molecule to measure the binding energies of near-threshold vibrational levels of the $X~^{2}\Sigma_{1/2}^{+}$ molecular ground state. We report results for $^{133}$Cs$^{170}$Yb, $^{133}$Cs$^{173}$Yb and $^{133}$Cs$^{174}$Yb, in each case determining the energy of several vibrational levels including the least-bound state. We fit an interaction potential based on electronic structure calculations to the binding energies for all three isotopologs and find that the ground-state potential supports 77 vibrational levels. We use the fitted potential to predict the interspecies s-wave scattering lengths for all seven Cs+Yb isotopic mixtures.

Structure, spectroscopy and cold collisions of the (SrNa)+ ionic system

We perform a study on extended adiabatic potential energy curves of nearly 38 states of 1,3$\Sigma^+$, 1,3$\Pi$ and 1,3$\Delta$ symmetries for the (SrNa)$^+$ ion, though only the ground and first two excited states are used for the study of scattering processes. Full Interaction Configuration (CI) calculations are carried out for this molecule using the pseudopotential approach. In this context, it is considered that two active electrons interact with the ionic cores and all single and double excitations were included in the CI calculations. A correction including the core-core electron interactions is also considered. Using the accurate potential energy data, the ground state scattering wave functions and cross sections are obtained for a wide range of energies. We find that, in order to get convergent results for the total scattering cross sections for energies of the order 1 K, one need to take into account at least 87 partial waves. In the low energy limit ( < 1 mK), elastic scattering cross sections exhibit Wigner law threshold law behavior while in the high energy limit the cross sections go as $E^{-1/3}$. A qualitative discussion about the possibility of forming the cold molecular ion by photoassociative spectroscopy is presented.