Role of dipole image forces in molecular adsorption

Electrostatic charge-charge and dipole-dipole interactions near the surface of a medium with screening non-locality (Review Article)

“…Actually, it is a function of k and should tend to unity at k → ∞ [27,29,37]. The raised issue of convergence due to the quantum-mechanical nature of screening is similar to that concerning the dipole image force energy saturation at the interface, which was considered earlier [32,33].…”

“…(28) only in the limit 0 m ε >> ε , i.e., for the extremely strong screening in the substrate (the perfectconductor model). Since, actually, the screening ability of the Thomas-Fermi metal is weaker than that of the perfect conductor, a correction term with the opposite sign appears in asymptotics (32). We emphasize that in the general case of arbitrary constants m ε and 0 ε , the dipole-dipole interaction substantially differs from the classical case.…”

“…Several adequate models have been proposed not only for plasma-like media (metals, doped semiconductors, electrolyte solutions) [29,37,53,[77][78][79] but also for media with bound electrons (insulators, intrinsic semiconductors) [80][81][82][83]. The quantum-mechanical character of ( ) ε k [84,85] was shown to be important in surface problems [25,27,32,33,86]. However, the main features of the nonlocal electrostatics can be understood on the basis of the simple quasi-classical models based on the Pauli principle and applied to metals [78,87] or semiconductors [80,81].…”

“…All other possible qq′-combinations give us the interaction energy between the constituents within the same dipoles, as well as the dipole image force energies, which was considered earlier [32,33,113].…”

“…However, in the vicinity of a metal or semiconductor surface, classical electrostatics fails, and non-local electro-statics elaborated for layered structures has to be applied [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. In other words, the spatial dispersion of the substrate dielectric functions (i.e., the non-local character of charge and dipole screening in the medium) should be taken into account.…”