It has long been assumed that dipole-bound anionic states possess two properties;,(i) the electron binding energy is dominated by the electrostatic electron-dipole interaction, and (ii) the geometrical distortion of the polar molecule upon attachment of a distant electron is negligible. Our results indicate, however, that the dispersion interaction between the loosely bound electron and the electrons of the neutral dimer is as important as the electrostatic electron-dipole stabilization. In addition, the hydrogen bond in (HF) is susceptible to a deformation upon attachment of a distant electron. This deformation enhances both the electrostatic and dispersion components of the electron binding energy. The calculated Franck-Condon factors indicate that neutral dimers formed in electron photodetachment experiments may be vibrationally excited in both stiff intramolecular HF stretching modes and soft intermolecular modes. The predicted value of the adiabatic electron detachment energy for (HF)(2)(-) is 396 cm(-1) and the theoretical photoelectron spectrum is in remarkable agreement with the experimental data of Bowen et. al. J. H. Hendricks, H. L. de Clercq, S. A. Lyapustina, and K. H. Bowen, Jr. [J. Chem. Phys. 107, 2962 (1997)]. (C) 1997 American Institute of Physics.