Before we proceed further we wish to highlight a problem that arises in most quantum chemistry applications. In studying quantum systems, such as MW, which are composed out of atomic building blocks, it is customary to solve the problem by expressing the electron's wavefunction in terms of the atomic orbitals on the various atoms. A problem that arises is that these orbitals are not usually orthogonal to each other. Including this nonorthogonality complicates the solution and so it is often neglected. In the analysis that follows we have utilized a transformation which removes the nonorthogonality and allows for a straightforward solution. This transformation leads to an energy dependent Hamiltonian which will play an important role in determining the presence of antiresonances.
The LS equation we consider has the form
Here is the scattered electron wavefunction of the transformed Hamiltonian HE. WE couples the molecule to the adjacent lead sites. is the initial electron state which is a propagating Bloch wave that is confined to the left lead. G'(E)=(E - H0E)-1 is the Green's function of the decoupled system.
We consider the LS equation in the tight binding approximation
and solve for
This gives us the value for
which is the value of the wavefunction on the first
atomic site on the right lead. The transmission probability,
T is simply
The result is
The sum over j is over only the MO's. In the above, WE1,j = H1,j - E S1,j is the energy-dependent hopping element of HE between the first lead site and the jth MO in terms of the hopping element of the original Hamiltonian H and the overlap S in the non-orthogonal basis. The Green's function on the molecule is expanded in terms of its molecular eigenstates and this gives for the jth MO with energy . G'1,1 is the diagonal matrix element of the Green's function G'(E) at the end site of the isolated lead.
Antiresonances of the MW occur where the
transmission T is equal to zero. These occur at Fermi
energies E that are the roots of Eq. (7), namely
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