High Resolution Image Download MS PowerPoint Slide This study presents a theoretical investigation of the potential energy curves (PECs) and spectroscopic constants of the NaMg + molecular cation using the intermediate Hamiltonian Fock space coupled-cluster method with singles and doubles within the (2,0) sector [IH-FS-CCSD(2,0)]. The NaMg + cation has gained scientific interest due to its potential applications in ultracold chemistry, yet it remains experimentally unexplored. We computed 20 lowest-lying PECs and assigned them to 10 dissociation limits. Our results demonstrated high accuracy, and computed curves are smooth and continuous over the entire range of interatomic distances. The study validates the effectiveness of the IH-FS-CCSD(2,0) method in describing PECs of diatomic molecular cations composed of alkali and alkaline earth metals and provides a solid theoretical foundation for further studies of NaMg + and similar systems.
High Resolution Image Download MS PowerPoint Slide This study presents a theoretical investigation of the potential energy curves (PECs) and spectroscopic constants of the NaMg + molecular cation using the intermediate Hamiltonian Fock space coupled-cluster method with singles and doubles within the (2,0) sector [IH-FS-CCSD(2,0)]. The NaMg + cation has gained scientific interest due to its potential applications in ultracold chemistry, yet it remains experimentally unexplored. We computed 20 lowest-lying PECs and assigned them to 10 dissociation limits. Our results demonstrated high accuracy, and computed curves are smooth and continuous over the entire range of interatomic distances. The study validates the effectiveness of the IH-FS-CCSD(2,0) method in describing PECs of diatomic molecular cations composed of alkali and alkaline earth metals and provides a solid theoretical foundation for further studies of NaMg + and similar systems.
Studies of anions are inherently more challenging than investigations of neutrals and cations because of the diffuse and weakly bound character of an anionic electron. Here, we present a comprehensive computational examination of ground-state diatomic molecular anions composed of alkali-metal (Li, Na, K, Rb, Cs, Fr) and alkaline-earth-metal (Be, Mg, Ca, Sr, Ba, Ra) atoms. We study 21 alkali-metal diatomic anions in the X2Σ+ electronic state and 36 alkali-metal--alkaline-earth-metal diatomic anions in the X1Σ+ electronic state. The calculations employ a hierarchy of the coupled cluster methods, combined with large Gaussian basis sets and small-core relativistic energy-consistent pseudopotentials for heavier elements. We compute potential energy curves, permanent electric dipole moments, and static polarizabilities, and we assess convergence and uncertainties of our results. Additionally, using the multireference configuration interaction and equation-of-motion electron-attachment coupled cluster methods, we investigate excited electronic states of alkali-metal molecular anions, including valence-bound and dipole-bound states. We predict crossings between ground neutral and excited anionic states, which may enhance resonant electron attachment and subsequent anion dissociation. This finding may be relevant for experiments with mixtures of ultracold ground-state alkali-metal molecules and Rydberg atoms.
High Resolution Image Download MS PowerPoint Slide Alkaline-earth-metal monohydrides M H ( M = Be, Mg, Ca, Sr, Ba) have long been regarded as promising candidates toward laser cooling and trapping; however, their rich internal level structures that are amenable to magneto-optical trapping have not been completely explored. Here, we first systematically evaluated Franck–Condon factors of these alkaline-earth-metal monohydrides in the A 2 Π 1/2 ← X 2 Σ + transition, exploiting three respective methods (the Morse potential, the closed-form approximation, and the Rydberg–Klein–Rees method). The effective Hamiltonian matrix was introduced for MgH, CaH, SrH, and BaH individually in order to figure out their molecular hyperfine structures of X 2 Σ +, the transition wavelengths in the vacuum, and hyperfine branching ratios of A 2 Π 1/2 ( J ′ = 1/2,+) ← X 2 Σ + ( N = 1,−), followed by possible sideband modulation proposals to address all hyperfine manifolds. Lastly, the Zeeman energy level structures and associated magnetic g factors of the ground state X 2 Σ + ( N = 1,−) were also presented. Our theoretical results here not only shed more light on the molecular spectroscopy of alkaline-earth-metal monohydrides toward laser cooling and magneto-optical trapping but also can contribute to research in molecular collisions involving few-atom molecular systems, spectral analysis in astrophysics and astrochemistry, and even precision measurement of fundamental constants such as the quest for nonzero detection of electron’s electric dipole moment.
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.
We investigate the lifetimes of vibrational states of diatomic alkali-alkaline-earth cations to determine their suitability for ultracold experiments where long decoherence time and controllability by an external electric field are desirable. The potential energy and permanent dipole moment curves for the ground electronic states of LiBe+, LiMg+, NaBe+, and NaMg+ are obtained using the coupled cluster with singles doubles and triples and multireference configuration interaction methods in combination with large all-electron cc-pCVQZ and aug-cc-pCV5Z basis sets. The energies and wave functions of all vibrational states are obtained by solving the Schrödinger equation for nuclei with the B-spline basis set method. To predict the lifetimes of vibrational states, the transition dipole moments, as well as the Einstein coefficients describing spontaneous emission, and the stimulated absorption and emission induced by black body radiation are calculated. Surprisingly, in all studied ions, the lifetimes of the highest excited vibrational states are similar to the lifetimes of the ground vibrational states indicating that highly vibrationally excited ions could be useful for the ultracold experiments requiring long decoherence time.
A simple approximate version of the Fock-space relativistic coupled-cluster method is developed and applied for modeling the spin-orbit-coupling effect in the ${A}^{1}{\mathrm{\ensuremath{\Sigma}}}_{(u)}^{+}$ and ${b}^{3}{\mathrm{\ensuremath{\Pi}}}_{(u)}$ states of the heavy alkali diatomics RbCs and Cs2. Numerical stability in a wide range of molecular geometries is achieved at the cost of a very moderate loss of accuracy for low-lying states and negligibly small deviations of the computational scheme from strict size consistency. The adiabatic potential energy curves computed for the (2,3)0+ (RbCs) and (1,2)0u+ (Cs2) states are converted into ``quasidiabatic'' potentials and effective spin-orbit-coupling functions via projection of the scalar relativistic states onto the subsets of fully relativistic states. A detailed comparison of the present ab initio results with their experimental and preceding theoretical counterparts is performed.
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.