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The Journal of Chemical Physics

Ultracold photoassociative spectroscopy of heteronuclear alkali-metal diatomic molecules

He Wang, William C. Stwalley

Published Apr 8, 1998• 123 citations
Publisher

Abstract

We have examined and identified the excited long-range Hund’s case (c) molecular states of the ten heteronuclear alkali metal diatomic molecules which support bound states and can be probed by ultracold photoassociative spectroscopy. Analytical expressions for the heteronuclear long-range free-bound Franck–Condon factors as a function of the internuclear distance R and the vibrational quantum number v are derived and discussed. The KRb system has considerably stronger excited long-range interactions than any other heteronuclear alkali diatomic molecule and has very favorable Franck–Condon factors for the photoassociation process. The heteronuclear photoassociative spectroscopy will provide spectroscopic measurements of the binary elastic scattering lengths of heteronuclear cold collisions which are the crucial parameters for sympathetic cooling of mixed atomic gases.

DOI
10.1063/1.475987

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We have examined and identified the excited long-range Hund’s case (c) molecular states of the ten heteronuclear alkali metal diatomic molecules which support bound states and can be probed by ultracold photoassociative spectroscopy. Analytical expressions for the heteronuclear long-range free-bound Franck–Condon factors as a function of the internuclear distance R and the vibrational quantum number v are derived and discussed. The KRb system has considerably stronger excited long-range interactions than any other heteronuclear alkali diatomic molecule and has very favorable Franck–Condon factors for the photoassociation process. The heteronuclear photoassociative spectroscopy will provide spectroscopic measurements of the binary elastic scattering lengths of heteronuclear cold collisions which are the crucial parameters for sympathetic cooling of mixed atomic gases.
The pure long-range 1u{1}_{u}1u​ state of an alkali-metal dimer is observed in 39K2{}^{39}{\mathrm{K}}_{2}39K2​ using photoassociative spectroscopy of ultracold atoms. High-resolution spectra for vibrational levels $v=\stackrel{\ensuremath{\rightarrow}}{0}7$ are recorded by resonance-enhanced two-photon ionization. Strong rotation-hyperfine couplings are observed. Major molecular constants and a hyperfine structure analysis are presented. This 1u{1}_{u}1u​ state is useful as an ungerade Franck-Condon ``window'' at large internuclear distance for studies of highly excited long-range interactions.
Photoassociation is the process in which two colliding atoms absorb a photon to form an excited molecule. The development of laser-cooling techniques for producing gases at ultracold (<1mK)(<1\phantom{\rule{0.3em}{0ex}}\mathrm{mK})(<1mK) temperatures allows photoassociation spectroscopy to be performed with very high spectral resolution. Of particular interest is the investigation of molecular states whose properties can be related, with high precision, to the properties of their constituent atoms with the ``complications'' of chemical binding accounted for by a few parameters. These include bound long-range or purely long-range vibrational states in which two atoms spend most or all of their time at large internuclear separations. Low-energy atomic scattering states also share this characteristic. Photoassociation techniques have made important contributions to the study of all of these. This review describes what is special about photoassociation spectroscopy at ultracold temperatures, how it is performed, and a sampling of results including the determination of scattering lengths, their control via optical Feshbach resonances, precision determinations of atomic lifetimes from molecular spectra, limits on photoassociation rates in a Bose-Einstein condensate, and briefly, production of cold molecules. Discussions are illustrated with examples on alkali-metal atoms as well as other species. Progress in the field is already past the point where this review can be exhaustive, but an introduction is provided on the capabilities of photoassociation spectroscopy and the techniques presently in use.
The high-resolution rovibronic spectroscopies of cold and ultracold molecules (e.g. supersonic molecular beam excitation spectra (MB), photoassociation spectra of ultracold atoms (PA), resonance-enhanced multiphoton ionization spectra (REMPI), stimulated Raman transfer (SRT) spectra) are of major current interest. This manuscript summarizes the significant level of understanding of these various spectroscopies, enabled by using simple graphical and semiclassical ideas and shortcuts. Physical realizations of these spectroscopies will be illustrated using the alkali metal diatomic molecules, both homonuclear (e.g. Rb2) and heteronuclear (e.g. KRb).
Abstract Ultracold photoassociation is typically performed at large internuclear separations, where the scattering wavefunction amplitude is large and Franck–Condon overlap is maximized. Recently, work by this group and others on alkali-metal diatomics has shown that photoassociation can efficiently form molecules at short internuclear distance in both homonuclear and heteronuclear dimers. We propose that this short-range photoassociation is due to excitation near the wavefunction amplitude maximum at the inner wall of the lowest triplet potential. We show that Franck–Condon factors (FCFs) from the highest-energy bound state can almost precisely reproduce FCFs from a low-energy scattering state, and that both calculations match experimental data from the near-zero positive-energy scattering state with reasonable accuracy. We also show that the corresponding photoassociation from the inner wall of the ground-state singlet potential at much shorter internuclear distance is weaker and undetectable under our current experimental conditions. We predict from FCFs that the strongest of these weaker short-range photoassociation transitions are one order of magnitude below our current sensitivity.
We present spectroscopic studies of ultracold LiRb molecules using ionization detection. The molecules are created by cooling and trapping Li and Rb atoms in overlapping magneto-optical traps (MOTs) and using light resonant with a free-bound transition to create weakly bound excited state molecules in a process known as photoassociation (PA). We explore weakly bound vibrational levels of LiRb with PA spectroscopy using ionization detection and, where possible, compare our results with earlier measurements performed in our lab using trap-loss spectroscopy. In addition, we also probe vibrational levels of the ground triplet electronic state and excited electronic states using resonantly enhanced multiphoton ionization (REMPI) spectroscopy. We identify several vibrational levels of the α3Σ+, (3)3ΠΩ and (4)3Σ + states and compare our observations with theoretical calculations. As LiRb is one of the least studied heteronuclear diatomic molecules, these studies are aimed towards exploring the molecular structure. The spectroscopic work is also in line with the long-term project goals of transferring ultracold LiRb molecules into the lowest rotational and vibrational levels of the ground singlet electronic state. Molecules in this rovibronic ground state possess a large electric dipole moment, which is essential for application of ultracold molecules in various quantum computation schemes. The rovibronic ground state will also be an ideal starting point for investigating molecular entangled states.
We report on the observation of photoassociation resonances in ultracold collisions between ^{23}Na^{40}K molecules and ^{40}K atoms. We perform photoassociation in a long-wavelength optical dipole trap to form deeply bound triatomic molecules in electronically excited states. The atom-molecule Feshbach resonance is used to enhance the free-bound Franck-Condon overlap. The photoassociation into well-defined quantum states of excited triatomic molecules is identified by observing resonantly enhanced loss features. These loss features depend on the polarization of the photoassociation lasers, allowing us to assign rotational quantum numbers. The observation of ultracold atom-molecule photoassociation resonances paves the way toward preparing ground-state triatomic molecules, provides a new high-resolution spectroscopy technique for polyatomic molecules, and is also important to atom-molecule Feshbach resonances.