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1. Relativistic aspects of orbital and magnetic anisotropies in the chemical bonding and structure of lanthanide molecules

   https://doi.org/10.1088/1367-2630/ac1a9a  

   Tiesinga, Eite ; Kłos, Jacek ; Li, Ming ; Petrov, Alexander ; Kotochigova, Svetlana ( August 2021 , New Journal of Physics)

   Abstract The electronic structure of magnetic lanthanide atoms is fascinating from a fundamental perspective. They have electrons in a submerged open 4f shell lying beneath a filled 6s shell with strong relativistic correlations leading to a large magnetic moment and large electronic orbital angular momentum. This large angular momentum leads to strong anisotropies, i. e. orientation dependencies, in their mutual interactions. The long-ranged molecular anisotropies are crucial for proposals to use ultracold lanthanide atoms in spin-based quantum computers, the realization of exotic states in correlated matter, and the simulation of orbitronics found in magnetic technologies. Short-ranged interactions and bond formation among these atomic species have thus far not been well characterized. Efficient relativistic computations are required. Here, for the first time we theoretically determine the electronic and ro-vibrational states of heavy homonuclear lanthanide Er 2 and Tm 2 molecules by applying state-of-the-art relativistic methods. In spite of the complexity of their internal structure, we were able to obtain reliable spin–orbit and correlation-induced splittings between the 91 Er 2 and 36 Tm 2 electronic potentials dissociating to two ground-state atoms. A tensor analysis allows us to expand the potentials between the atoms in terms of a sum of seven spin–spin tensor operators simplifying future research. The strengths of the tensor operators as functions of atom separation are presented and relationships among the strengths, derived from the dispersive long-range interactions, are explained. Finally, low-lying spectroscopically relevant ro-vibrational energy levels are computed with coupled-channels calculations and analyzed. 

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2. Quantum Metrology with a Molecular Lattice Clock and State-Selected Photodissociation of Ultracold Molecules

   Lee, C.-H. ( January 2020 , Columbia University thesis)

   Over the past few decades, rapid development of laser cooling techniques and narrow-linewidth lasers have allowed atom-based quantum clocks to achieve unprecedented precision. Techniques originally developed for atomic clocks can be extended to ultracold molecules, with applications ranging from quantum-state-controlled ultracold chemistry to searches for new physics. Because of the richness of molecular structure, quantum metrology based on molecules provides possibilities for testing physics that is beyond the scope of traditional atomic clocks. This thesis presents the work performed to establish a state-of-the-art quantum clock based on ultracold molecules. The molecular clock is based on a frequency difference between two vibrational levels in the electronic ground state of 88Sr2 diatomic molecules. Such a clock allows us test molecular QED, improve constraints on nanometer-scale gravity, and potentially provide a model-independent test of temporal variations of the proton-electron mass ratio. Trap-insensitive spectroscopy is crucial for extending coherent molecule-light interactions and achieving a high quality factor Q. We have demonstrated a magic wavelength technique for molecules by manipulating the optical lattice frequency near narrow polarizability resonances. This general technique allows us to increase the coherence time to tens of ms, an improvement of a factor of several thousand, and to narrow the linewidth of a 25 THz vibrational transition initially to 30 Hz. This width corresponds to the quality factor Q = 8 × 10^11. Besides the molecular quantum metrology, investigations of novel phenomena in state-selected photodissociation are also described in this thesis, including magnetic-field control of photodissociation and observation of the crossover from ultracold to quasiclassical chemistry. 

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3. The Li + CaF → Ca + LiF chemical reaction under cold conditions

   https://doi.org/10.1039/d3cp01464a  

   da Silva, Humberto ; Yao, Qian ; Morita, Masato ; Kendrick, Brian K. ; Guo, Hua ; Balakrishnan, Naduvalath ( May 2023 , Physical Chemistry Chemical Physics)

   The calcium monofluoride (CaF) molecule has emerged as a promising candidate for precision measurements, quantum simulation, and ultracold chemistry experiments. Inelastic and reactive collisions of laser cooled CaF molecules in optical tweezers have recently been reported and collisions of cold Li atoms with CaF are of current experimental interest. In this paper, we report ab initio electronic structure and full-dimensional quantum dynamical calculations of the Li + CaF → LiF + Ca chemical reaction. The electronic structure calculations are performed using the internally contracted multi-reference configuration-interaction method with Davidson correction (MRCI + Q). An analytic fit of the interaction energies is obtained using a many-body expansion method. A coupled-channel quantum reactive scattering approach implemented in hyperspherical coordinates is adopted for the scattering calculations under cold conditions. Results show that the Li + CaF reaction populates several low-lying vibrational levels and many rotational levels of the product LiF molecule and that the reaction is inefficient in the 1–100 mK regime allowing sympathetic cooling of CaF by collisions with cold Li atoms. 

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4. Non-local thermodynamic equilibrium analysis of the methylidyne radical molecular lines in metal-poor stellar atmospheres

   https://doi.org/10.1051/0004-6361/202245503  

   Popa, S. A. ; Hoppe, R. ; Bergemann, M. ; Hansen, C. J. ; Plez, B. ; Beers, T. C. ( February 2023 , Astronomy & Astrophysics)

   Aims. An analysis of the methylidyne (CH) radical in non-local thermodynamic equilibrium (NLTE) is performed for the physical conditions of cool stellar atmospheres typical of red giants (log ɡ = 2.0, T eff = 4500 K) and the Sun. The aim of the present work is to explore whether the G band of the CH molecule, which is commonly used in abundance diagnostics of carbon-enhanced metal-poor stars, is sensitive to NLTE effects. Methods. LTE and NLTE theoretical spectra were computed with the MULTI code. We used one-dimensional (1D) LTE hydrostatic MARCS model atmospheres with parameters representing eleven red giant stars with metallicities ranging from [Fe/H] = −4.0 to [Fe/H] = 0.0 and carbon-to-iron ratios of [C/Fe] = 0.0, +0.7, +1.5, and +3.0. The CH molecule model was represented by 1981 energy levels, 18 377 radiative bound-bound transitions, and 932 photo-dissociation reactions. The rates due to transitions caused by collisions with free electrons and hydrogen atoms were computed using classical recipes. Results. Our calculations suggest that NLTE effects in the statistical equilibrium of the CH molecule are significant and cannot be neglected for precision spectroscopic analysis of C abundances. The NLTE effects are mostly driven by radiative over-dissociation, owing to the very low dissociation threshold of the molecule and significant resonances in the photo-dissociation cross-sections. The NLTE effects in the G band increase with decreasing metallicity. When comparing the C abundances determined from the CH G band in LTE and in NLTE, we show that the C abundances are always under-estimated if LTE is assumed. The NLTE corrections to C abundance inferred from the CH feature range from +0.04 dex for the Sun to +0.21 dex for a red giant with metallicity [Fe/H] = −4.0. Conclusions. Departures from the LTE assumption in the CH molecule are non-negligible, and NLTE effects have to be taken into account in the diagnostic spectroscopy based on the CH lines. We show here that the NLTE effects in the optical CH lines are non-negligible for the Sun and red giant stars, but further calculations are warranted to investigate the effects in other regimes of stellar parameters. 

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5. Non-adiabatic quantum interference in the ultracold Li + LiNa → Li 2 + Na reaction

   https://doi.org/10.1039/d0cp05499b  

   Kendrick, Brian K. ; Li, Hui ; Li, Ming ; Kotochigova, Svetlana ; Croft, James F. ; Balakrishnan, Naduvalath ( March 2021 , Physical Chemistry Chemical Physics)

   null (Ed.)

   Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li 2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers. 

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