Two valence bond mechanisms for electron conduction along a linear chain of six or eight lithium atoms are studied using an ab initio valence bond approach. The initial step is of the type (-)(LiALiB)(LiCLiD)(LiELiF)(...)(+) --> (-)(LiALiB)(+)(LiCLiD)(-)(LiELiF)(...)(+), in which the transferred electron occupies either the 2psigma(C) atomic orbital (Pauling mechanism) or the antibonding sigma*(CD) molecular orbital. An external potential is modeled by use of negative and positive charges located to the left and to the right of the chain of atoms. It is calculated that (-)(LiLi)(+)(LiLi)(-)(LiLi)(...)(+) --> (-)(LiLi)(LiLi)(+)(LiLi)-...(+), which involves electron and positive hole transfer, as well as (-)(LiLi)(+)(LiLi)(-)(LiLi)(...)(+) --> (-)(LiLi)(+)(LiLi)(LiLi)(-)(...)(+), with electron transfer only, contribute to the second electron transfer process. Resonance between the valence bond structures associated with the second step helps lower the energy of the second step of either mechanism. The antibonding molecular orbital mechanism is calculated to involve a marginally lower energy than the Pauling mechanism. The resonance stabilization that occurs in the second step is concomitant with greater positive hole delocalization than the first step. This phenomenon is illustrated for a linear polyene by use of Huckel molecular orbital theory and the free electron model for electrons in a 1-dimensional box. For both eight-atom mechanisms, the propensity for electron transfer to occur between cathode and anode increases as the size of the external potential increases.