Diabatic wave functions

It is important to note that the two surface calculations will be carried out in the diabatic representation. One can get the initial diabatic wave function matrix for the two surface calculations using the above adiabatic initial wave function by the following orthogonal transformation,... 

The key to get a diabatic electronic state is a strict constraint i.e. keep local symmetry elements invariant. For ethylene, let us start from the cis con-former case. The nuclear geometry of the attractor must be on the (y,z)-plane according to Fig.l. The reaction coordinate must be the dis-rotatory displacement. Due to the nature of the LCAO-MO model in quantum computing chemistry, the closed shell filling of the HOMO must change into a closed shell of the LUMO beyond 0=n/4. The symmetry of the diabatic wave function is hence respected. Mutatis mutandis, the trans conformer wave function before n/4 corresponds to a double filling of the LUMO beyond the n/4 point on fills the HOMO twice. At n/4 there is the diradical singlet and triplet base wavefunctions. 

We discuss the FCD method for hole transfer a generalization to other cases of charge transfer is straightforward [41]. The (real) diabatic wave functions and (j)a are assumed to be normalized and completely localized on donor and acceptor, respectively. Furthermore, the adiabatic states ij/i and ij/z of the... 

The non-diagonal matrix element from diabatic wave functions and total... 

Using the semiclassical solution of Eq.(28) for the amplitudes in p -representation, we can obtain the diabatic wave functions in x -representation as... 

By taking into account the direction of steepest descent, the asymptotic diabatic wave functions at x —> OC can be expressed as a sum of contributions from... 

The second reason pertains to chemical interpretation usually any of the diabatic wave functions are chosen as corresponding to a particular electronic distribution (chemical bond pattern) in the system, and from Eq. (6.42), we may recognize what kind of chemical structure dominates Thus, using the diabatic basis, there is a chance of gaining insight into the chemistry going on in the system. ... 

The quantity 5 in the above equation is the reactive scattering matrix from an initial state (i) of the reactant to a final state (/) of the product. In terms of the component diabatic wave functions [Eq. (14)], the above equation can be rewritten as... 

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