Selecting molecules in the vibrational and rotational ground state by deflection

A beam of diatomic molecules scattered off a standing wave laser mode splits according to the rovibrational quantum state of the molecules. Our numerical calculation shows that single state resolution can be achieved by properly tuned, monochromatic light. The proposed scheme allows for selecting non-vibrating and non-rotating molecules from a thermal beam, implementing a laser Maxwell's demon to prepare a rovibrationally cold molecular ensemble. Received 23 August 2000 and Received in final form 17 November 2000     

Blackbody-radiation-assisted laser cooling of molecular ions

The translational motion of molecular ions can be effectively cooled sympathetically to temperatures below 100 mK in ion traps through Coulomb interactions with laser-cooled atomic ions. The distribution of internal rovibrational states, however, gets in thermal equilibrium with the typically much higher temperature of the environment within tens of seconds. We consider a concept for rotational cooling of such internally hot, but translationally cold, heteronuclear diatomic molecular ions. The scheme relies on a combination of optical pumping from a few specific rotational levels into a "dark state" with redistribution of rotational populations mediated by blackbody radiation.     

Dark resonances for ground-state transfer of molecular quantum gases

One possible way to produce ultra-cold, high-phase-space-density quantum gases of molecules in the rovibronic ground state is given by molecule association from quantum-degenerate atomic gases on a Feshbach resonance and subsequent coherent optical multi-photon transfer into the rovibronic ground state. In ultra-cold samples of Cs₂ molecules, we observe two-photon dark resonances that connect the intermediate rovibrational level |v=73,J=2〉 with the rovibrational ground state |v=0,J=0〉 of the singlet X ¹ Σ _g ⁺ ground-state potential. For precise dark resonance spectroscopy we exploit the fact that it is possible to efficiently populate the level |v=73,J=2〉 by two-photon transfer from the dissociation threshold with the stimulated Raman adiabatic passage (STIRAP) technique. We find that at least one of the two-photon resonances is sufficiently strong to allow future implementation of coherent STIRAP transfer of a molecular quantum gas to the rovibrational ground state |v=0,J=0〉.     

Creating, detecting and locating ultracold molecules in a surface trap

Ultracold molecules have been produced by photoassociation of Cs atoms trapped in a mirror magneto-optical trap. The molecules were detected by resonantly enhanced multi-photon ionization followed by time-of-flight mass spectroscopy. The time-of-flight ofatomic and molecular ions was investigated in the presence of a dc bias voltageapplied to the conducting mirror. This technique provides a new tool for determining the distance between the cold molecules and the mirror surface. This revised version was published online in August 2005 with a corrected cover date.     

Diagnosis of negative hydrogen ions and rovibrational distribution of H<Subscript>2</Subscript> molecule in non-thermal plasmas

Rovibrational excited hydrogen molecule plays an important role for the production of H^- ions. The correlation between H^- ion density and rovibrational distribution of H₂ molecules has been investigated in dielectric barrier discharge hydrogen plasmas via optical emission spectrometry and molecular beam mass spectrometry. The relative vibrational distribution of molecular hydrogen in the electronic ground state has been determined by the best fitting to the Fulcher-α band emission lines. It is shown that the ratio of the Q_(0-0)(1) to Q_(1-1)(1) line is very suitable and simple for the diagnosis of vibrational temperature in the range of 1500 to 7500 K. At certain discharge conditions (ac 40 kHz, 14 kV), the vibrational temperature decreases from 3600 to 2400 K as the pressure increases from 100 to 200 Pa and the negative ions density near the ground electrode also decreases as the pressure increases. Both the hydrogen ions density and the vibrational temperature increase with the increasing of discharge voltage. It is found that the evolution of negative atomic hydrogen ions density greatly depends on the vibrational temperature.     

Coherent transfer of photoassociated molecules into the rovibrational ground state

We report on the direct conversion of laser-cooled 41K and 87Rb atoms into ultracold 41K87Rb molecules in the rovibrational ground state via photoassociation followed by stimulated Raman adiabatic passage. High-resolution spectroscopy based on the coherent transfer revealed the hyperfine structure of weakly bound molecules in an unexplored region. Our results show that a rovibrationally pure sample of ultracold ground-state molecules is achieved via the all-optical association of laser-cooled atoms, opening possibilities to coherently manipulate a wide variety of molecules.     

Pulse shaping and its characterization of mid-infrared femtosecond pulses: Toward coherent control of molecules in the ground electronic states

We have examined a technique of complex shaping of mid-infrared femtosecond laser pulses towards accurate and precise control of rovibrational wave packets of molecules in the ground electronic state. A Germanium acousto-optics modulator was used as a device for the pulse shaping. In order to characterize the shaped pulses precisely, sum-frequency cross-correlation frequency-resolved optical gating was introduced for the analysis of both amplitude and phase of the electric fields. The mid-infrared pulses were shaped and characterized with a frequency resolution better than 4.5 cm⁻¹. Such a resolution is supposed to be sufficient for the realization of quantum gate operations with high fidelity, which is one of the most challenging applications of rovibrational wave packet manipulation of molecules. In order to demonstrate the precision of our method of shaping and its characterization, we have generated shaped pulses that will realize Hadamard and NOT quantum gates with rovibrational states of a CO molecule.     

Generating molecular rovibrational coherence by two-photon femtosecond photoassociation of thermally hot atoms

The formation of diatomic molecules with rotational and vibrational coherence is demonstrated experimentally in free-to-bound two-photon femtosecond photoassociation of hot atoms. In a thermal gas at a temperature of 1000 K, pairs of magnesium atoms, colliding in their electronic ground state, are excited into coherent superpositions of bound rovibrational levels in an electronically excited state. The rovibrational coherence is probed by a time-delayed third photon, resulting in quantum beats in the UV fluorescence. A comprehensive theoretical model based on ab initio calculations rationalizes the generation of coherence by Franck-Condon filtering of collision energies and partial waves, quantifying it in terms of an increase in quantum purity of the thermal ensemble. Our results open the way to coherent control of a binary reaction.     

超冷极性分子

目前对超冷原子的研究已经从最初的原子分子物理扩展到了物理的很多分支.极性分子可以将电偶极相互作用引入到超冷体系,同时分子又与原子类似,可以灵活地被光和其他电磁场操控,因而很多理论工作都预言了超冷极性分子在超冷化学、量子模拟和量子信息等领域会有重要的应用.但由于超冷基态分子的制备非常困难,如何把超冷物理从原子发展到分子还是一个方兴未艾的课题.过去的10年间,各种分子冷却技术都取得了很大突破,本文回顾了这些进展,并着重介绍了基于异核冷原子的磁缔合结合受激拉曼转移这一技术,该技术在制备高密度的基态碱金属超冷极性分子上取得了较大的成功.本文也总结了超冷极性碱金属分子基本碰撞特性研究的一些实验结果.     

Stark-potential evaporative cooling of polar molecules in a novel optical-access opened electrostatic trap

We propose a novel optical-access opened electrostatic trap to study the Stark-potential evaporative cooling of polar molecules by using two charged disk electrodes with a central hole of radius r0= 1.5 mm, and derive a set of new analytical equations to calculate the spatial distributions of the electrostatic field in the above charged-disk layout. Afterwards, we calculate the electric-field distributions of our electrostatic trap and the Stark potential for cold ND3 molecules, and analyze the dependences of both the electric field and the Stark potential on the geometric parameters of our charged-disk scheme,and find an optimal condition to form a desirable trap with the same trap depth in the x, y, and z directions. Also, we propose a desirable scheme to realize an efficient loading of cold polar molecules in the weak-field-seeking states, and investigate the dependences of the loading efficiency on both the initial forward velocity of the incident molecular beam and the loading time by Monte Carlo simulations. Our study shows that the maximal loading efficiency of our trap scheme can reach about 95%, and the corresponding temperature of the trapped cold molecules is about 28.8 m K. Finally, we study the Stark-potential evaporative cooling for cold polar molecules in our trap by the Monte Carlo method, and find that our simulated evaporative cooling results are consistent with our developed analytical model based on trapping-potential evaporative cooling.     

Probing harpooning and dissociation in gas–surface reactions by exoemission

2 and N₂O with Cs are discussed. If the molecules interact with a metal surface the nonadiabaticity is triggered by harpooning, i.e. resonant ionization and acceleration in the image field, and subsequent dissociation. From recent experiments with state-selected N₂O molecules on Cs [1] the range of harpooning reactions is extended. From exoemission of N₂O in the first excited bending mode and its suppression in the ground state, it is concluded that a molecular affinity level may be lowered by more than 3.5 eV in front of a metallic Cs surface. This is a hint that harpooning is more common than expected. Received: 24 March 1998/Accepted: 21 August 1998     

Observation of ultracold ground-state heteronuclear molecules

We report the observation of translationally ultracold heteronuclear ground-state molecules in a two-species magneto-optical trap containing 39K and 85Rb atoms. The KRb molecules are produced via photoassociation and detected by multiphoton ionization. We had characterized their temperature and measured their formation rate constant. We believe that the two-species trap could be used as a reliable source of ultracold molecules to be captured by electrostatic, magnetic, or optical traps. This possibility will certainly motivate further investigation of quantum collective effects as well as high-resolution spectroscopy of the rovibrational level structure of cold heteronuclear molecular systems.     

Ultracold triplet molecules in the rovibrational ground state

We report here on the production of an ultracold gas of tightly bound Rb2 triplet molecules in the rovibrational ground state, close to quantum degeneracy. This is achieved by optically transferring weakly bound Rb2 molecules to the absolute lowest level of the ground triplet potential with a transfer efficiency of about 90%. The transfer takes place in a 3D optical lattice which traps a sizeable fraction of the tightly bound molecules with a lifetime exceeding 200 ms.     

Superconducting microwave cavity towards controlling the motion of polar molecules

We propose the use of superconducting microwave cavities for the focusing and deceleration of cold polar molecular beams. A superconducting cavity with a high quality factor produces a large ac Stark shift in polar molecules, which allow us to efficiently control molecular motion. Our discussion is based on the experimental characterization of a prototype cavity: a lead–tin-coated cylindrical copper cavity, which has a quality factor of 10⁶ and tolerates several watts of input power. Such a microwave device provides a powerful way to control molecules not only in low-field-seeking states, but also in high-field-seeking states such as the ground rotational state.     

Theoretical analysis of the coupling between Feshbach states and hyperfine excited states in the creation of ~(23)Na~(40)K molecule

We present an intensive study of the coupling between different Feshbach states and the hyperfine levels of the excited states in the adiabatic creation of ~(23)Na~(40)K ground-state molecules.We use coupled-channel method to calculate the wave function of the Feshbach molecules,and give the short-range wave function of triplet component.The energies of the hyperfine excited states and the coupling strength between the Feshbach states and the hyperfine excited states are calculated.Our results can be used to prepare a specific hyperfine level of the rovibrational ground state to study the ultracold collisions involving molecules.     

Production of ultracold, polar RbCs* molecules via photoassociation

We have produced ultracold, polar RbCs* molecules via photoassociation in a laser-cooled mixture of Rb and Cs atoms. Using a model of the RbCs* molecular interaction which reproduces the observed rovibrational structure, we infer decay rates in our experiments into deeply bound X(1)Sigma(+) ground-state RbCs vibrational levels as high as 5 x 10(5) s(-1) per level. Population in such deeply bound levels could be efficiently transferred to the vibrational ground state using a single stimulated Raman transition, opening the possibility to create large samples of stable, ultracold polar molecules.     

Modelling rotations,vibrations, and rovibrational couplings in astructural molecules – a case study based on the H+5 molecular ion

One-dimensional (1D) and two-dimensional (2D) models are investigated, which help to understand the unusual rovibrational energy-level structure of the astronomically relevant and chemically interesting astructural molecular ion H⁺₅. Due to the very low hindering barrier characterising the 1D torsion-only vibrational model of H⁺₅, this model yields strongly divergent energy levels. The results obtained using a realistic model for the torsion potential, including the computed (near) degeneracies, can be rationalised in terms of the model with no barrier. Coupling of the torsional motion with a single rotational degree of freedom is also investigated in detail. It is shown how the embedding-dependent rovibrational models yield energy levels that can be rationalised via the 2D vibrational model containing two independent torsions. Insight into the complex rovibrational energy level structure of the models and of H⁺₅ is gained via variational nuclear motion and diffusion Monte Carlo computations and by the analysis of the wavefunctions they provide. The modelling results describing the transition from the zero barrier limit to the large barrier limit should prove to be useful for the important class of molecules and molecular ions that contain two weakly coupled internal rotors.     

Two-color photoionization and photoelectron studies by combining infrared and vacuum ultraviolet

Recent developments of two-color infrared (IR)-vacuum ultraviolet (VUV) and VUV-IR photoionization and photoelectron detection schemes for spectroscopic studies are described. By preparing molecules in selected rovibrational states by IR excitation prior to VUV-photoionization, state-selected and state-to-state photoionization cross sections can be obtained by IR-VUV-photoionization efficiency (IR-VUV-PIE) and IR-VUV-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) measurements, respectively. Rotationally resolved autoionizing Rydberg states converging to excited ionic states, which cannot be observed by single-photon VUV-PIE measurements, can be examined by the IR-VUV-PIE scheme. By monitoring the photoion and the PFI-PE intensities at a fixed VUV energy as a function of IR frequency, the respective IR photoion and IR absorption spectra of the corresponding neutral molecule can be measured. Two-color VUV-IR photo-induced Rydberg ionization (PIRI) experiment, in which high-n Rydberg states are prepared by VUV-photoexcitation followed by IR-induced autoionization, has also been demonstrated. Since the IR-VUV-PIE, IR-VUV-PFI-PE, and VUV-IR-PIRI methods do not require the existence of a bound intermediate electronic state in the UV and are generally applicable to all molecules, the development of these two-color photoionization and photoelectron schemes is expected to significantly enhance the scope of VUV spectroscopy and chemistry.     

Population redistribution in optically trapped polar molecules

We investigate the rovibrational population redistribution of polar molecules in the electronic ground state induced by spontaneous emission and blackbody radiation. As a model system we use optically trapped LiCs molecules formed by photoassociation in an ultracold two-species gas. The population dynamics of vibrational and rotational states is modeled using an ab initio electric dipole moment function and experimental potential energy curves. Comparison with the evolution of the v″ = 3 electronic ground state yields good qualitative agreement. The analysis provides important input to assess applications of ultracold LiCs molecules in quantum simulation and ultracold chemistry.     

Single- and multi-photon absorption of carbon dioxide laser lines by SO2 and CO2 molecules

Summary We have used 60 rovibrational lines of a Lumonics TEA CO₂ laser to record the spectra of coincidence of SO₂ IR absorption with CO₂ laser emission. We extended the same type of investigation to CO₂ molecules and observed an absorption at practically all the rovibrational lines of the laser. We have also recorded the increase of absorption with pressure of the studied molecule and with its temperature. Our work reveals very accurately the fine structure of these absorptions that shows a clear discreteness in the intensities of the lines. Some implication of this discreteness in multiphoton absorption is also presented, through data that indicate very strong vibrational coupling between ground and excited electronic states of SO₂. The authors of this paper have agreed to not receive the proofs for correction.