Ground-state energy, infinite metallic

Equation (5.21) is based on the electrochemical way of counting the energy difference between zero (defined throughout this book as the potential energy of an electron at its ground state at "infinite" distance from the metal) and the Fermi level Ep (Eq. 5.15). The latter quantity must not be confused with the Fermi energy go which is the energy difference between... 

Ground-state Energy of an Infinite Metallic Hydrogen Chain... 

Fig. 19 Schematic level diagram around the Fermi level, for the infinite DNA wire studied by Gervasio et al. [94]. The Fermi level positioned in the middle of the gap was chosen as the zero of energy. The highest occupied "band" is constituted of a manifold of 12 states localized on the 12 Gua bases contained in the periodic unit and originated from the Gua-HOMO. Gyt-localized states (n Cyt) appear as another manifold at 3.16 eV above the HOMO-band. Flowever, empty electron states due to metal counterions and phosphates are revealed at 1.28 eV above the FIOMO-band (see also [92]), and the ground-to-excited-state transitions are therefore related to charge transfer between the inner and outer helix (adapted from [94] with permission Copyright 2002 by the American Physical Society)...

Several requirements have been put forward in order to model chemisorption processes in infinite surfaces with metal clusters. The ground state wave function should have a conduction band near the Fermi level with significant amplitude near the chemisorption site. The cluster should exhibit a high density of states and should be highly polarizable. It should also possess an ionization potential similar to that of the bulk. Finally, the orbital structure of the cluster employed in the model must be in a suitable bonding state, which is often not the ground state. However, this rule implies that it is not important to describe the density of states, the ionization potential, or, the polarizability of the bulk with the cluster system in order to obtain stable chemisorption energies. 

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