Electronic wave function determination

By using the determinant fomi of the electronic wave functions, it is readily shown that a phase-inverting reaction is one in which an even number of election pairs are exchanged, while in a phase-preserving reaction, an odd number of electron pairs are exchanged. This holds for Htickel-type reactions, and is demonstrated in Appendix A. For a definition of Hilckel and Mbbius-type reactions, see Section III. 

The electronic wave functions and potential energy can be determined in ways similai to those done in the first and second order. Here we wish to emphasize that, the full wave function in this order is... 

We now consider planar molecules. The electronic wave function is expressed with respect to molecule-fixed axes, which we can take to be the abc principal axes of inertia, namely, by taking the coordinates (x,y,z) in Figure 1 coincided with the principal axes (a, b, c). In order to determine the parity of the molecule through inversions in SF, we first rotate all the displacement vectors... 

The simplest many-electron wave function that satisfies the Exclusion Principle is a product of N different one-electron functions that have been antisymmetrized, or written as a determinant. Here, N is the number of electrons (or valence electrons) in the molecule. HyperChem uses this form of the wave function for most semi-empirical and ab initio calculations. Exceptions involve using the Configuration Interaction option (see page 119). HyperChem computes one-electron functions, termed molecular spin orbitals, by relatively simple integration and summation calculations. The many-electron wave function, which has N terms (the number of terms in the determinant), never needs to be evaluated. 

For some systems a single determinant (SCFcalculation) is insufficient to describe the electronic wave function. For example, square cyclobutadiene and twisted ethylene require at least two configurations to describe their ground states. To allow several configurations to be used, a multi-electron configuration interaction technique has been implemented in HyperChem. 

In developing perturbation theory it was assumed that the solutions to the unpermrbed problem formed a complete set. This is general means that there must be an infinite number of functions, which is impossible in actual calculations. The lowest energy solution to the unperturbed problem is the HF wave function, additional higher energy solutions are excited Slater determinants, analogously to the Cl method. When a finite basis set is employed it is only possible to generate a finite number of excited determinants. The expansion of the many-electron wave function is therefore truncated. 

Approximating a many-electron wave function by a finite sum of Slater determinants, e.g. truncating the Cl, CC or MBPT wave function to include only certain excitation types. 

Electron Nuclear Dynamics (48) departs from a variational form where the state vector is both explicitly and implicitly time-dependent. A coherent state formulation for electron and nuclear motion is given and the relevant parameters are determined as functions of time from the Euler equations that define the stationary point of the functional. Yngve and his group have currently implemented the method for a determinantal electronic wave function and products of wave packets for the nuclei in the limit of zero width, a "classical" limit. Results are coming forth protons on methane (49), diatoms in laser fields (50), protons on water (51), and charge transfer (52) between oxygen and protons. 

The Hartree-Fock description of the hydrogen molecule requires two spinorbitals, which are used to build the single-determinant two-electron wave function. In the Restricted Hartree-Fock method (RHF) these two spinorbitals are created from the same spatial... 

It is determined by the overlap of the electron wave functions of the donor, qip, and acceptor, 9, and by the interaction V of the electron with the acceptor. 

As discussed above, it is impossible to solve equation (1-13) by searching through all acceptable N-electron wave functions. We need to define a suitable subset, which offers a physically reasonable approximation to the exact wave function without being unmanageable in practice. In the Hartree-Fock scheme the simplest, yet physically sound approximation to the complicated many-electron wave function is utilized. It consists of approximating the N-electron wave function by an antisymmetrized product4 of N one-electron wave functions (x ). This product is usually referred to as a Slater determinant, OSD ... 

To understand how Kohn and Sham tackled this problem, we go back to the discussion of the Hartree-Fock scheme in Chapter 1. There, our wave function was a single Slater determinant SD constructed from N spin orbitals. While the Slater determinant enters the HF method as the approximation to the true N-electron wave function, we showed in Section 1.3 that 4>sd can also be looked upon as the exact wave function of a fictitious system of N non-interacting electrons (that is electrons which behave as uncharged fermions and therefore do not interact with each other via Coulomb repulsion), moving in the elfective potential VHF. For this type of wave function the kinetic energy can be exactly expressed as... 

Werner Heisenberg stated that the exact location of an electron could not be determined. All measuring technigues would necessarily remove the electron from its normal environment. This uncertainty principle meant that only a population probability could be determined. Otherwise coincidence was the determining factor. Einstein did not want to accept this consequence ("God does not play dice"). Finally, Erwin Schrodinger formulated the electron wave function to describe this population space or probability density. This equation, particularly through the work of Max Born, led to the so-called "orbitals". These have a completely different appearance to the clear orbits of Bohr. 

In the Hartree-Fock or self-consistent field picture, 4> also enters the Schrodinger equation which determines the electronic wave functions. One thus has to solve the Schrodinger equation... 

Thus, for a planar interface one determines the one-electron wave functions according to... 

---