The H$_2^+$ molecular ion: low-lying states

Abstract

Matching for a wavefunction the WKB expansion at large distances and Taylor expansion at small distances leads to a compact, few-parametric uniform approximation found in {\it J. Phys. B44, 101002 (2011)}. The ten low-lying eigenstates of H$_2^+$ of the quantum numbers $(n,m,\La,\pm)$\, with $n=m=0$ at $\La=0,1,2$, with $n=1$, $m=0$ and $n=0$, $m=1$ at $\La=0$ of both parities are explored for all interproton distances $R$. For all these states this approximation provides the relative accuracy $\lesssim 10^{-5}$ (not less than 5 s.d.) locally, for any real coordinate $x$ in eigenfunctions, when for total energy $E(R)$ it gives 10-11 s.d. for $R \in [0,50]$~a.u. Corrections to the approximation are evaluated in the specially-designed, convergent perturbation theory. Separation constants are found with not less than 8 s.d. The oscillator strength for the electric dipole transitions $E1$ is calculated with not less than 6~s.d. A dramatic dip in the $E1$ oscillator strength $f_{1s\si_g-3p\si_u}$ at $R \sim R_{eq}$ is observed. The magnetic dipole and electric quadrupole transitions are calculated for the first time with not less than 6~s.d. in oscillator strength. For two lowest states $(0,0,0,\pm)$ (or, equivalently, $1s\si_g$ and $2p\si_u$ states) the potential curves are checked and confirmed in the Lagrange mesh method within 12~s.d. Based on them the Energy Gap between $1s\si_g$ and $2p\si_u$ potential curves is approximated with modified Pade $R e^{-R} [Pade(8/7)](R)$ with not less than 4-5 figures at $R \in [0, 40]$\,a.u. Sum of potential curves $E_{1s\si_g} + E_{2p\si_u}$ is approximated by Pade $1/R [Pade(5/8)](R)$ in $R \in [0, 40]$\,a.u. with not less than {3-4} figures.