Path‐integral molecular‐dynamics calculation of the conduction‐band energy minimum V0 of excess electrons in fluid argon

Using path‐integral molecular‐dynamics simulations, we calculate the conduction‐band energy minimum V0 (relative to vacuum) of an excess electron injected in fluid argon over a range of densities (n) from the gas phase to the liquid near the triple point. An accurate pseudopotential is employed to represent the electron–argon interaction. Special attention is paid to the convergence on the number of beads of the isomorphic electron polymer chain, the simulation‐box size, and the question of ergodicity. The calculated V0(n) values are in very good agreement with experimental data. As a result of the very extended character of the excess electron state at all fluid densities considered, the precise value of V0 is shown to be only weakly sensitive to the degree of disorder and the coordination number of the fluid. Relaxation effects are also found to be negligible. These results account for the success of the mean‐field approximation afforded by the Wigner‐Seitz V0(n) calculations for the heavy rare‐gas flui...