Enhanced positron annihilation on polyatomic molecules is a long-standing and complex problem. We report the results of calculations of resonant positron annihilation on methyl halides. A free parameter of our theory is the positron binding energy. A comparison with energy-resolved annihilation rates measured for CH$_3$F, CH$_3$Cl, CH$_3$Br [Barnes et al. Phys. Rev. A {\bf 74}, 012706 (2006)] shows good agreement and yields estimates of the binding energies.
We demonstrate Feshbach optimized photoassociation (FOPA) into the $0_{g}^{-} (5$S$_{1/2}+5$P$_{1/2}$) state in $^{85}$Rb$_{2}$. FOPA uses the enhancement of the amplitude of the initial atomic scattering wave function due to a Feshbach resonance to increase the molecular formation rate from photoassociation. We observe three vibrational levels, $v=$127, 140, and 150, with previously unmeasured binding energies of 256, 154, and 96 cm$^{-1}$. We measure the frequency, central magnetic field position, and magnetic field width of each Feshbach resonance. Our findings experimentally confirm that t…
Measurements of energy-resolved positron-molecule annihilation show the existence of positron binding and vibrational Feshbach resonances. The existing theory describes this phenomenon successfully for the case of infrared-active vibrational modes which allow dipole coupling between the incident positron and the vibrational motion. Presented here are measurements of positron-molecule annihilation made using a recently developed cryogenic positron beam capable of significantly improved energy resolution. The results provide evidence of resonances associated with infrared-inactive vibrational mo…
The dominant mechanism of low-energy positron annihilation in polyatomic molecules is through positron capture in vibrational Feshbach resonances (VFR). In this paper we investigate theoretically the effect of anharmonic terms in the vibrational Hamiltonian on the positron annihilation rates. Such interactions enable positron capture in VFRs associated with multiquantum vibrational excitations, leading to enhanced annihilation. Mode coupling can also lead to faster depopulation of VFRs, thereby reducing their contribution to the annihlation rates. To analyze this complex picture, we use couple…
We present precise measurements of the optical Feshbach resonances (OFRs) of $^{174}$Yb atoms for the intercombination transition. We measure the photoassociation (PA) spectra of a pure $^{174}$Yb Bose-Einstein condensate, and determine the dependence of OFRs to PA laser intensities and frequencies for four least bound vibrational levels near the intercombination transition. We confirm that our measurements are consistent with the temporal decay of a BEC subjected to a PA beam in the vicinity of the fourth vibrational level from the dissociation limit.
A method is proposed for detecting positron-atom bound states by observing enhanced positron annihilation due to electronic Feshbach resonances at electron-volt energies. The method is applicable to a range of open-shell transition metal atoms which are likely to bind the positron: Fe, Co, Ni, Tc, Ru, Rh, Sn, Sb, Ta, W, Os, Ir, and Pt. Estimates of their binding energies are provided.
This article presents an overview of current understanding of the interaction of low-energy positrons with molecules with emphasis on resonances, positron attachment and annihilation. Annihilation rates measured as a function of positron energy reveal the presence of vibrational Feshbach resonances (VFR) for many polyatomic molecules. These resonances lead to strong enhancement of the annihilation rates. They also provide evidence that positrons bind to many molecular species. A quantitative theory of VFR-mediated attachment to small molecules is presented. It is tested successfully for select…
We report on the measurement and analysis of photoionisation, mass-analysed-threshold-ionisation and pulsed-field-ionisation zero-kinetic-energy photoelectron spectra of HD in the vicinity of the dissociative-ionisation thresholds H$^+$ + D(1s) + e$^-$ and H(1s) + D$^+$ + e$^-$. The spectra were recorded via the $v=11$-13 vibrational levels of the $\bar{\rm H}$ and $\bar{\rm B}$ outer wells of the H$\bar{\rm H}$~$^1Σ_g^+$ and B$^{\prime\prime}\bar{\rm B}$~$^1Σ_u^+$ states and provide information on the weakly bound levels of the X$^+$ $^2Σ_g^+$ ground state of HD$^+$ with vibrational quantum n…
Relativistic coupled-cluster single-double approximation is used to calculate positron-atom bound states. The method is tested on closed-shell atoms such as Be, Mg, Ca, Zn, Cd, and Hg where a number of accurate calculations is available. It is then used to calculate positron binding energies for a range of open-shell transition metal atoms from Sc to Cu, from Y to Pd, and from Lu to Pt. These systems possess Feshbach resonances, which can be used to search for positron-atom binding experimentally through resonant annihilation or scattering.
The aim of this work is to identify the mechanisms responsible for very large rates and other peculiarities observed in low-energy positron annihilation on molecules. The two mechanisms considered are: (i) Direct annihilation of the incoming positron with one of the molecular electrons. This mechanism dominates for atoms and small molecules. I show that its contribution to the annihilation rate can be related to the positron elastic scattering cross section. This mechanism is characterized by strong energy dependence of the annihilation rate at small positron energies if a low-lying virtual le…
The model-potential approach previously developed by the authors to study positron interactions with molecules is used to calculate the positron binding energy for $n$-alkanes (C$_n$H$_{2n+2}$) and the corresponding cycloalkanes (C$_n$H$_{2n}$). For $n$-alkanes, the dependence of the binding energy on the conformation of the molecule is investigated, with more compact structures showing greater binding energies. As a result, thermally averaged binding energies for larger alkanes ($n\gtrsim 9$) show a strong temperature dependence in the range of 100-600 K. This suggests that positron resonant …
We study collision of two atoms with formation of Feshbach resonance at combined interaction with the external magnetic field and laser radiation. In cases of one- and two-photon resonances of laser radiation with two discrete vibrational molecular levels, we show that Feshbach resonances appear at interaction of external magnetic field with dressed states formed via Autler-Townes effect. In addition, in case of one-photon resonance the lower vibrational molecular state is coupled by laser radiation with the continuum of the elastic channel and forms laser-induced Feshbach resonance via both A…
We report on the formation of ultracold fermionic Feshbach molecules of $^{23}$Na$^{40}$K, the first fermionic molecule that is chemically stable in its ground state. The lifetime of the nearly degenerate molecular gas exceeds 100 ms in the vicinity of the Feshbach resonance. The measured dependence of the molecular binding energy on the magnetic field demonstrates the open-channel character of the molecules over a wide field range and implies significant singlet admixture. This will enable efficient transfer into the singlet vibrational ground state, resulting in a stable molecular Fermi gas …
Compared to purely atomic collisions, ultracold collisions involving molecules have the potential to support a much larger number of Fano-Feshbach resonances due to the huge amount of ro-vibrational states available. In order to handle such ultracold atom-molecule collisions, we formulate a theory that incorporates the ro-vibrational Fano-Feshbach resonances in a statistical manner while treating the physics of the long-range scattering, which is sensitive to such things as hyperfine states, collision energy and any applied electromagnetic fields, exactly within multichannel quantum defect the…
Low-energy positron scattering from metastable helium
Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences（中国科学院精密测量科学与技术创新研究院）；University of Chinese Academy of Sciences（中国科学院大学）
We report the creation of ultracold bosonic $^{23}$Na$^{87}$Rb Feshbach molecules via magneto-association. By ramping the magnetic field across an interspecies Feshbach resonance, at least 4000 molecules can be produced out of the near degenerate ultracold mixture. Fast loss due to inelastic atom-molecule collisions is observed, which limits the pure molecule number, after residual atoms removal, to 1700. The pure molecule sample can live for 21.8(8) ms in the optical trap, long enough for future molecular spectroscopy studies toward coherently transferring to the singlet ro-vibrational ground…
The energies at geometries close to the equilibrium for the e$^+$BeO and e$^+$LiF ground states were computed by means of diffusion Monte Carlo simulations. These results allow us to predict the equilibrium geometries and the vibrational frequencies for these exotic systems,and to discuss their stability with respect to the various dissociation channels. Since the adiabatic positron affinities were found to be smaller than the dissociation energies for both complexes, we propose these two molecules as possible candidates in the challenge to produce and detect stable positron-molecule systems.
Two-color photoassociation of ground state $^6$Li$^{87}$Rb molecules via the $\mathrm{B}^1Π$ electronic state using short pulses near a magnetic Feshbach resonance is studied theoretically. A near-resonant magnetic field is applied to mix the hyperfine singlet and triplet components of the initial wave function and enhance the photoassociation rate, before the population is transferred to the ground state by a second pulse. We show that an increase of up to three orders of magnitude in the absolute number of molecules produced is attainable for deeply bound vibrational levels. This technique c…
We study the process of low-energy electron capture by the SF6 molecule. Our approach is based on the model of Gauyacq and Herzenberg [J. Phys. B 17, 1155 (1984)] in which the electron motion is coupled to the fully symmetric vibrational mode through a weakly bound or virtual s state. By tuning the two free parameters of the model, we achieve an accurate description of the measured electron attachment cross section and good agreement with vibrational excitation cross sections of the fully symmetric mode. An extension of the model provides a limit on the characteristic time of intramolecular vi…
We present the results of an experimental and theoretical study of the electronically excited $\tripletex$ state of $^{87}$Rb$_2$ molecules. The vibrational energies are measured for deeply bound states from the bottom up to $v'=15$ using laser spectroscopy of ultracold Rb$_2$ Feshbach molecules. The spectrum of each vibrational state is dominated by a 47\,GHz splitting into a $\cog$ and $\clg$ component caused mainly by a strong second order spin-orbit interaction. Our spectroscopy fully resolves the rotational, hyperfine, and Zeeman structure of the spectrum. We are able to describe to first…
Large anomalous shifts of potassium-39 Feshbach resonances
Swinburne University of Technology（斯威本科技大学）；CSIRO（联邦科学与工业研究组织）；Instytut Fizyki Teoretycznej, Uniwersytet Jagielloński（雅盖隆大学理论物理研究所）；Österreichische Academie der Wissenschaften（奥地利科学院）；Institut für Quantenoptik und Quanteninformation (IQOQI)（量子光学与量子信息研究所）；Universität Innsbruck（因斯布鲁克大学）
The B-spline basis set method is applied to determining the rovibrational eigen-spectrum of diatomic molecules. A particular attention is paid to a challenging numerical task of an accurate and efficient description of the vibrational levels near the dissociation limit (halo-state and Feshbach molecules). Advantages of using B-splines are highlighted by comparing the performance of the method with that of the commonly-used discrete variable representation (DVR) approach. Several model cases, including the Morse potential and realistic potentials with 1/R^3 and 1/R^6 long-range dependence of th…
We have performed high-resolution two-photon dark-state spectroscopy of an ultracold gas of Rb molecules in the triplet ground state at a magnetic field of about 1000 G. The vibrational ladder as well as the hyperfine and low-lying rotational structure is mapped out. Energy shifts in the spectrum are observed due to singlet-triplet mixing at binding energies as deep as a few hundred GHz x h. This information together with data from other sources is used to optimize the potentials of the triplet and singlet states in a coupled-channel model. We find that the hyperfine structure depends weakly o…
We show that weakly-bound molecules can be probed by "shaking" in a pulsed nonresonant laser field. The field introduces a centrifugal term which expels the highest vibrational level from the potential that binds it. Our numerical simulations applied to the Rb$_2$ and KRb Feshbach molecules indicate that shaking by feasible laser pulses can be used to accurately recover the square of the vibrational wavefunction and, by inversion, also the long-range part of the molecular potential.
Positron cooling via inelastic collisions in CF$_4$ and N$_2$ gases is simulated, including positron-positron interactions. Owing to the molecular symmetries, cooling is assumed to be chiefly due to energy loss via vibrational (rotational) excitations for CF$_4$ (N$_2$). For CF$_4$, it is found that the inclusion of the dipole-inactive $ν_1$ mode, in addition to the dipole-active modes $ν_3$ and $ν_4$, can provide room-temperature thermalization and an accurate cooling timescale. Combination cooling enabled by the $ν_1$ mode, and positron-positron interactions both contribute to the Maxwellian…
We have studied interspecies scattering in an ultracold mixture of $^{87}$Rb and $^{133}$Cs atoms, both in their lowest-energy spin states. The three-body loss signatures of 30 incoming s- and p-wave magnetic Feshbach resonances over the range 0 to 667 G have been catalogued. Magnetic field modulation spectroscopy was used to observe molecular states bound by up to 2.5 MHz$\times h$. Magnetic moment spectroscopy along the magneto-association pathway from 197 to 182 G gives results consistent with the observed and calculated dependence of the binding energy on magnetic field strength. We have c…
We discuss the role of the geometrical phase in predissociation dynamics of vibrational states near a conical intersection of two electronic potential surfaces of a D_{3h} molecule. For quantitative description of the predissociation driven by the coupling near a conical intersection, we developed a method for calculating lifetimes and positions of vibrational predissociated states (Feshbach resonances) for X_3 molecule. The method takes into account the two coupled three-body potential energy surfaces, which are degenerate at the intersection. As an example, we apply the method to obtain life…
We have calculated the isotropic $C\_6$ coefficients characterizing the long-range van der Waals interaction between two identical heteronuclear alkali-metal diatomic molecules in the same arbitrary vibrational level of their ground electronic state $X^1Σ^+$. We consider the ten species made up of $^7$Li, $^{23}$Na, $^{39}$K, $^{87}$Rb and $^{133}$Cs. Following our previous work [M.~Lepers \textit{et.~al.}, Phys.~Rev.~A \textbf{88}, 032709 (2013)] we use the sum-over-state formula inherent to the second-order perturbation theory, composed of the contributions from the transitions within the gr…
A problem to account for the direct electron-positron annihilation in positron-hydrogen scattering above the positronium formation threshold has been resolved within the time independent formalism. The generalization of the optical theorem is derived for the case when an absorption potential is present in the Hamiltonian. With this theorem the annihilation cross section is fully determined by scattering amplitudes. This allows us to separate out analytically the contribution of the positronium formation from the overall annihilation cross section. The rest is determined as the direct annihilat…
We report a high-resolution spectroscopic investigation of the long-range states of the $^{23}$Na$^{87}$Rb molecule near its Na($3^2S_{1/2}$)+Rb($5^2P_{3/2}$) asymptote. This study was performed with weakly bound ultracold molecules produced via magneto-association with an inter-species Feshbach resonance. We observed several regular vibrational series, which are assigned to the 5 attractive long-range states correlated with this asymptote. The vibrational levels of two of these states have sharp but complex structures due to hyperfine and Zeeman interactions. For the other states, we observed…
Compared to purely atomic collisions, ultracold molecular collisions potentially support a much larger number of Fano-Feshbach resonances due to the enormous number of ro-vibrational states available. In fact, for alkali-metal dimers we find that the resulting density of resonances cannot be resolved at all, even on the sub-$μ$K temperature scale of ultracold experiments. As a result, all observables become averaged over many resonances and can effectively be described by simpler, non-resonant scattering calculations. Two particular examples are discussed: non-chemically reactive RbCs and chem…
This review describes recent experimental and theoretical advances in forming molecules in ultracold gases of trapped alkali metal atoms, both by magnetic tuning through Feshbach resonances and by photoassociation. Molecular Bose-Einstein condensation of long-range states of both boson dimers and fermion dimers was achieved in 2002-3. Condensates of boson dimers were found to be short-lived, but long-lived condensates of fermion dimers have been produced. Signatures of triatomic and tetraatomic molecules have recently been observed. Both homonuclear and heteronuclear molecules have been formed…
We demonstrate the coherent creation of a single NaCs molecule in its rotational, vibrational, and electronic (rovibronic) ground state in an optical tweezer. Starting with a weakly bound Feshbach molecule, we locate a two-photon transition via the $|{c^3Σ,v'=26}\rangle$ excited state and drive coherent Rabi oscillations between the Feshbach state and a single hyperfine level of the NaCs rovibronic ground state $|{X^1Σ,v''=0,N''=0}\rangle$ with a binding energy of $D_0 = h \times 147038.30(2)$ GHz. We measure a lifetime of $3.4\pm1.6$ s for the rovibronic ground-state molecule, which possesses…
We present experimental observations of seven vibrational levels $v'=20-26$ of the $1^{3}Σ_{g}^{+}$ excited state of Li$_2$ molecules by the photoassociation (PA) of a degenerate Fermi gas of $^6$Li atoms. For each vibrational level, we resolve the rotational structure using a Feshbach resonance to enhance the PA rates from p-wave collisions. We also, for the first time, determine the spin-spin and spin-rotation interaction constants for this state. The absolute uncertainty of our measurements is $\pm 0.00002$ cm$^{-1}$ ($\pm 600$ kHz). We use these new data to further refine an analytic poten…
We report on a high-resolution spectroscopic survey of ${}^{6}\textrm{Li}{}^{40}\textrm{K}$ molecules near the $2\textrm{S}+4\textrm{P}$ dissociation threshold and produce a fully empirical representation for the $\textrm{B}^{1}Π$ potential by connecting available short- and long-range data. The purpose is to identify a suitable intermediate state for a coherent Raman transfer to the absolute ground state, and the creation of a molecular gas with dipolar interactions. Starting from weakly bound ultracold Feshbach molecules, the transition frequencies to twenty-six vibrational states are determ…
We report on the creation of ultracold 84Sr2 molecules in the electronic ground state. The molecules are formed from atom pairs on sites of an optical lattice using stimulated Raman adiabatic passage (STIRAP). We achieve a transfer efficiency of 30% and obtain 4x10^4 molecules with full control over the external and internal quantum state. STIRAP is performed near the narrow 1S0-3P1 intercombination transition, using a vibrational level of the 0u potential as intermediate state. In preparation of our molecule association scheme, we have determined the binding energies of the last vibrational l…
Optical Feshbach resonances [Phys. Rev. Lett. 94, 193001 (2005)] and pump-dump photoassociation with short laser pulses [Phys. Rev. A 73, 033408 (2006)] have been proposed as means to coherently form stable ultracold alkali dimer molecules. In an optical Feshbach resonance, the intensity and possibly frequency of a cw laser are ramped up linearly followed by a sudden switch-off of the laser. This is applicable to tightly trapped atom pairs. In short-pulse photoassociation, the pump pulse forms a wave-packet in an electronically excited state. The ensuing dynamics carry the wave-packet to short…
We report on high-resolution spectroscopy of ultracold fermionic \nak~Feshbach molecules, and identify a two-photon pathway to the rovibrational singlet ground state via a resonantly mixed \Bcres intermediate state. Photoassociation in a $^{23}$Na-$^{40}$K atomic mixture and one-photon spectroscopy on \nak~Feshbach molecules reveal about 20 vibrational levels of the electronically excited \ctrip state. Two of these levels are found to be strongly perturbed by nearby \Bsing states via spin-orbit coupling, resulting in additional lines of dominant singlet character in the perturbed complex {${\r…
We report on photoassociation spectroscopy probing the $c^3Σ_{1}^+$ potential of the bi-alkali NaCs molecule, identifying eleven vibrational lines between $v' = 0$ and $v' = 25$ of the excited $c^3Σ_{1}^+$ potential, and resolving their rotational and hyperfine structure. The observed lines are assigned by fitting to an effective Hamiltonian model of the excited state structure with rotational and hyperfine constants as free parameters. We discuss unexpected broadening of select vibrational lines, and its possible link to strong spin-orbit coupling of the $c^3Σ_{1}^+$ potential with the nearby…
The collision of two atoms is an intrinsic multi-channel (MC) problem as becomes especially obvious in the presence of Feshbach resonances. Due to its complexity, however, single-channel (SC) approximations, which reproduce the long-range behavior of the open channel, are often applied in calculations. In this work the complete MC problem is solved numerically for the magnetic Feshbach resonances (MFRs) in collisions between generic ultracold 6Li and 87Rb atoms in the ground state and in the presence of a static magnetic field B. The obtained MC solutions are used to test various existing as w…
We study the combination of hyperfine and Zeeman structure in the spin-orbit coupled $A^1Σ_u^+-b^3Π_u$ complex of $^{87}\textrm{Rb}_2$. For this purpose, absorption spectroscopy at a magnetic field around $B=1000\:\textrm{G}$ is carried out. We drive optical dipole transitions from the lowest rotational state of an ultracold Feshbach molecule to various vibrational levels with $0^+$ symmetry of the $A-b$ complex. In contrast to previous measurements with rotationally excited alkali-dimers, we do not observe equal spacings of the hyperfine levels. In addition, the spectra vary substantially for…
Positrons bind to molecules leading to vibrational excitation and spectacularly enhanced annihilation. Whilst positron binding energies have been measured via resonant annihilation spectra for $\sim$90 molecules in the past two decades, an accurate \emph{ab initio} theoretical description has remained elusive. Of the molecules studied experimentally, calculations exist for only 6, and for these, standard quantum chemistry approaches have proved severely deficient, agreeing with experiment to at best 25% accuracy for polar molecules, and failing to predict binding in nonpolar molecules. The mec…
Cold inelastic collisions of atoms or molecules are analyzed using very general arguments. In free space, the deactivation rate can be enhanced or suppressed together with the scattering length of the corresponding elastic collision via a Feshbach resonance, and by interference of deactivation of the closed and open channels. In reduced dimensional geometries, the deactivation rate decreases with decreasing collision energy and does not increase with resonant elastic scattering length. This has broad implications; e.g., stabilization of molecules in a strongly confining two-dimensional optical…
The complexity of ultrafast molecular photoionization presents an obstacle to the modelling of pump-probe experiments. Here, a simple optimized model of atomic rubidium is combined with a molecular dynamics model to predict quantitatively the results of a pump-probe experiment in which long range rubidium dimers are first excited, then ionized after a variable delay. The method is illustrated by the outline of two proposed feasible experiments and the calculation of their outcomes. Both of these proposals use Feshbach 87Rb2 molecules. We show that long-range molecular pump-probe experiments sh…
We report a computational study of the anion states of the resveratrol (RV) and resorcinol (RS) molecules, also investigating dissociative electron attachment (DEA) pathways. RV has well known beneficial effects in human health, and its antioxidant activity was previously associated with DEA reactions producing H$_2$. Our calculations indicate a valence bound state ($π^*_1$) and four resonances ($π^*_2$ to $π^*_5$) for that system. While the computed thermodynamical thresholds are compatible with DEA reactions producing H$_2$ at 0~eV, the well known mechanism involving vibrational Feshbach res…
