Ab initio properties of the NaLi molecule in the $a^3{\Sigma }^{+}$ electronic state

Abstract

Ultracold polar and magnetic ${}^{23}$Na${}^6$Li molecules in the rovibrational ground state of the lowest triplet $a^3{\Sigma }^{+}$ electronic state have been recently produced. Here, we calculate the electronic and rovibrational structure of these 14-electron molecules with spectroscopic accuracy ($<0.5$cm${}^{-1}$) using state-of-the-art ab initio methods of quantum chemistry. We employ the hierarchy of the coupled-cluster wave functions and Gaussian basis sets extrapolated to the complete basis set limit. We show that the inclusion of higher-level excitations, core-electron correlation, relativistic, QED, and adiabatic corrections is necessary to reproduce accurately scattering and spectroscopic properties of alkali-metal systems. We obtain the well depth, $D_e=229.9(5)$cm${}^{-1}$, the dissociation energy, $D_0=208.2(5)$cm${}^{-1}$, and the scattering length, $a_s=-84_{-41}^{+25}$bohr, in good agreement with recent experimental measurements. We predict the permanent electric dipole moment in the rovibrational ground state, $d_0=$0.167(1)debye. These values are obtained without any adjustment to experimental data, showing that quantum chemistry methods are capable of predicting scattering properties of many-electron systems, provided relatively weak interaction and small reduced mass of the system.

7 pages, 2 figures, 2 tables

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