Towards the analytic theory of Potential Energy Curves for diatomic molecules. Studying He${}_2^+$ and LiH diatomics as illustration (1904.06614v4)

Abstract: Following the first principles the elements of the analytic theory of potential curves for diatomic molecules (diatomics) are presented. It is based on matching the perturbation theory at small internuclear distances $R$ and multipole expansion at large distances, modified by instanton-induced trans-series for homonuclear case, with addition of the phenomenologically described equilibrium configuration, if exists. It leads to a new class of (generalized) meromorphic potentials (modified by exponential terms) with difference in degrees of polynomials in numerator and denominator equal to 4 (6) for positively charged (neutral) diatomics. As examples the He$_2^+$ and LiH diatomics in Born-Oppenheimer (adiabatic) approximation are considered. For ${}^{4}$He$_2^+$ (${}^{3}$He$_2^+$) diatomics it is found the approximate analytic expression for the potential energy curves (analytic PEC) $V(R)$ for the ground state $X^2 \Sigma_u^+$ and the first excited state $A^2 \Sigma_g^+$. It provides 3-4 s.d. correctly for distances $R \in [1, 10]$\,a.u. with some irregularities for $A^2 \Sigma_g^+$ PEC at small distances (much smaller than equilibrium distances) probably related to level crossings which may occur there. The analytic PEC for the ground state $X^2 \Sigma_u^+$ supports 829 (626) rovibrational states with 3-4 s.d. of accuracy in energy, which is only by 1 state less (more) than 830 (625) reported in the literature. In turn, the analytic PEC for the excited state $A^2 \Sigma_g^+$ supports all 9 reported weakly-bound rovibrational states. Entire rovibrational spectra is found in a single calculation using the code based on the Lagrange mesh method.