Electron electric-dipole-moment interaction constant for HfF+from relativistic correlated all-electron theory

Abstract

We present a rigorous method for accurate ab initio calculations of the electron electric-dipole-moment $\mathcal{P},\mathcal{T}$-odd interaction constant ${W}_{d}$. The approach uses configuration interaction wave functions and Dirac four-component spinors as one-particle basis functions, and the interaction constant ${W}_{d}$ is obtained as an expectation value over these correlated wave functions. We apply the method to the HfF${}^{+}$ molecular ion and determine spectroscopic constants for four low-lying electronic states. For one of these states ($\ensuremath{\Omega}=1$) we determine the effective electric field (${E}_{\mathrm{eff}}={W}_{d}\phantom{\rule{0.16em}{0ex}}\ensuremath{\Omega}$), which amounts to 23.3 GV/cm, correlating 34 valence and outer atomic core electrons and using wave-function expansions with nearly $5\ifmmode\times\else\texttimes\fi{}{10}^{8}$ coefficients.