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International Symposium on Molecular Spectroscopy (ISMS)

VIBRONIC TRANSITIONS IN THE X-Sr SERIES (X=Li, Na, K, Rb): ON THE ACCURACY OF NUCLEAR WAVEFUNCTIONS DERIVED FROM QUANTUM CHEMISTRY

Andreas Hauser, Wolfgang Ernst, Johann Valentin Pototschnig, Ralf Meyer

Published Jun 21, 2016• 0 citations
Publisher

Abstract

Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. The preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. On the theoretical side, highly accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. Particularly problematic is the correct description of potential features at large intermolecular distances. Franck-Condon overlap integrals for nuclear wavefunctions in barely bound vibrational states are extremely sensitive to inaccuracies of the potential at long range. In this study, we compare the predictions of common, wavefunction-based ab initio techniques for a known de-excitation mechanism in alkali-alkaline earth dimers. It is the aim to analyze the predictive power of these methods for a preliminary evaluation of potential cooling mechanisms in heteronuclear open shell systems which offer the experimentalist an electric as well as a magnetic handle for manipulation. The series of $X$-Sr molecules, with $X$ = Li, Na, K and Rb, has been chosen for a direct comparison. Quantum degenerate mixtures of Rb and Sr have already been produced,\footnote{B. Pasquiou, A. Bayerle, S. M. Tzanova, S. Stellmer, J. Szczepkowski, M. Parigger, R. Grimm, and F. Schreck, Phys. Rev. A, 2013, 88, 023601} making this combination very promising for the production of ultracold molecules.

DOI
10.15278/isms.2016.tk09

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Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. The preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. On the theoretical side, highly accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. Particularly problematic is the correct description of potential features at large intermolecular distances. Franck-Condon overlap integrals for nuclear wavefunctions in barely bound vibrational states are extremely sensitive to inaccuracies of the potential at long range. In this study, we compare the predictions of common, wavefunction-based ab initio techniques for a known de-excitation mechanism in alkali-alkaline earth dimers. It is the aim to analyze the predictive power of these methods for a preliminary evaluation of potential cooling mechanisms in heteronuclear open shell systems which offer the experimentalist an electric as well as a magnetic handle for manipulation. The series of XXX-Sr molecules, with XXX = Li, Na, K and Rb, has been chosen for a direct comparison. Quantum degenerate mixtures of Rb and Sr have already been produced,\footnote{B. Pasquiou, A. Bayerle, S. M. Tzanova, S. Stellmer, J. Szczepkowski, M. Parigger, R. Grimm, and F. Schreck, Phys. Rev. A, 2013, 88, 023601} making this combination very promising for the production of ultracold molecules.
Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)-- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.
Ultracold diatomic molecules find application in quantum studies ranging from controlled chemistry and precision measurement physics to quantum many-body simulation and potentially quantum computing. Accurate knowledge of molecular properties is required to guide and explain ongoing experiments. Here, in an extensive and comparative study, we theoretically investigate the electronic properties of the ground-state diatomic molecules composed of alkali-metal (Li, Na, K, Rb, Cs, Fr) and alkaline-earth-metal (Be, Mg, Ca, Sr, Ba, Ra) atoms. We study 78 heteronuclear and homonuclear diatomic combinations, including 21 alkali-metal molecules in the ${X}^{1}{\mathrm{\ensuremath{\Sigma}}}^{+}$ and ${a}^{3}{\mathrm{\ensuremath{\Sigma}}}^{+}$ electronic states, 36 alkali-metal--alkaline-earth-metal molecules in the ${X}^{2}{\mathrm{\ensuremath{\Sigma}}}^{+}$ electronic state, and 21 alkaline-earth-metal molecules in the ${X}^{1}{\mathrm{\ensuremath{\Sigma}}}^{+}$ electronic state. We calculate potential energy curves, permanent electric dipole moments, and polarizabilities using the hierarchy of coupled-cluster methods up to CCSDTQ with large Gaussian basis sets and small-core relativistic energy-consistent pseudopotentials. We collect and analyze corresponding spectroscopic constants. We estimate computational uncertainties and compare the present values with previous experimental and theoretical data to establish a different theoretical benchmark. The presented results should be useful for further application of the studied molecules in modern ultracold physics and chemistry experiments.
Ultracold molecules have recently attracted much attention because of their envisioned impact on both technology and fundamental science. The physics within them, i.e. their rich internal structure, and between them, i.e. long-range interactions, offer an increased complexity compared to atoms, while allowing for full experimental quantum control of the relevant degrees of freedom. A promising method of production consists of a first stage, whereby the component atoms are trapped and cooled to ultracold temperatures, and a second stage, whereby these are associated into dimers. In particular, the ability of cooling alkaline-earth (AE) elements, besides more traditional alkalis (A), has put production of AE-AE and A-AE molecules within experimental reach. Homonuclear ground-state AE-AE, because of their insensitivity to external electric and magnetic fields, have been proposed for metrology and precision measurements. In this work we investigate efficient production of Sr dimers starting from either an atomic Mott-insulator or Bose-Einstein condensate. Heteronuclear ground-state A-AE would allow for novel few-body and many-body physics experiments. In this thesis we investigate production schemes for RbSr dimers, which oweing to their large electric and magnetic dipole moments and heavy mass, are ideal candidates for the attainment of quantum degeneracy and subsequent experiments. We show our results from optical spectroscopy and combine them with thermal fluorescence data from our collaborators in Warsaw to derive the ground-state potential energy curve. Finally, we report on the experimental observation of magnetic Fano-Feshbach resonances between Rb and Sr and argue for their applicability to efficient molecule production.
Alkaline-earth dimers are now been used, as new grounds for, testing fundamental physics laws, precision measurements and quantum computation. As a starting point for such experiments, one needs a very good knowledge of the electronic structure, energetics and long-range behavior of these molecular ions. We perform accurate ab initio calculations for the ground and low-lying excited states of Be2+, Mg2+, Ca2+ and Sr2+ molecular ions. We have also calculated the spectroscopic constants, electronic transition dipole moments, polarizabilities and long-range dispersion coefficients for the various alkaline-earth ionic dimers. We have extended our calculations to study heteronuclear species of alkaline-earth molecular ions, like BeCa+, and also mixed alkali alkaline-earth species like NaCa+. We calculated photoassociation (PA) pathways for formation of cold molecular ions and also studied corrections to the Born-Oppenheimer Hamiltonian: non-adiabatic couplings and hyperfine structure due to nuclear spins and electric quadrupoles. We believe, this work would lay foundation, not only for new experiments in ultracold physics and chemistry, but would also provide valuable starting point for theoretical calculations involving low temperature scattering and resonant charge transfer.
Quantum gases of doubly polar molecules represent appealing frameworks for a variety of cross-disciplinary applications, encompassing quantum simulation and computation, controlled quantum chemistry, and precision measurements. Through a joint experimental and theoretical study, here we explore a novel class of ultracold paramagnetic polar molecules combining lithium alkali and chromium transition metal elements. Focusing on the specific bosonic isotopologue 6 Li 53 Cr , leveraging on the Fermi statistics of the parent atomic mixture and on suitable Feshbach resonances recently discovered, we produce up to 50 × 10 3 ultracold Li Cr molecules at peak phase-space densities exceeding 0.1, prepared within the least bound rotationless level of the Li Cr electronic ground state X 6 Σ + . By also developing new probing methods, we thoroughly characterize the molecular gas, demonstrating the paramagnetic nature of Li Cr dimers and the precise control of their quantum state. We investigate their stability against inelastic processes and identify a parameter region where pure Li Cr samples exhibit lifetimes exceeding 0.2 s. Parallel to this, we employ state-of-the-art quantum chemical calculations to accurately predict the properties of Li Cr ground and excited electronic states. This model, able to reproduce the experimental Li - Cr high-spin, scattering length, allows us to identify both efficient paths to coherently transfer weakly bound Li Cr dimers to their absolute ground state, and suitable transitions for their subsequent optical manipulation. Our studies establish Li - Cr as a prime candidate to realize ultracold gases of doubly polar molecules with significant electric (3.3 D) and magnetic ( 5 μ B ) dipole moments. Published by the American Physical Society 2024
states. As first outcomes of our analysis, we calculate the s-wave scattering properties for all stable isotopic combinations and corroborate the locations of Fano-Feshbach resonances between alkali Rb and closed-shell Sr atoms recently observed [V. Barbéet al., Nat. Phys., 2018, 14, 881]. These results and more generally our strategy should greatly contribute to the generation of ultracold alkali-alkaline-earth dimers, whose applications range from quantum simulation to state-controlled quantum chemistry.