The electronic Hamiltonian

If V is the total Coulombic potential between all the nuclei and electrons in the system, then, in the absence of any spin-dependent terms, the electronic Hamiltonian is given by... 

The electronic Hamiltonian and the comesponding eigenfunctions and eigenvalues are independent of the orientation of the nuclear body-fixed frame with respect to the space-fixed one, and hence depend only on m. The index i in Eq. (9) can span both discrete and continuous values. The q ) form... 

Traditionally, for molecular systems, one proceeds by considering the electronic Hamiltonian which consists of the quantum mechanical operators for the kinetic energy of the electrons, their mutual Coulombic repulsions, and... 

The adiabatic picture is the standard one in quantum chemistry for the reason that, not only is it mathematically well defined, but it is also that used in ab initio calculations, which solve the electronic Hamiltonian at a particular nuclear geometry. To see the effects of vibronic coupling on the potential energy surfaces one must move to what is called a diabatic representation [1,65,180, 181]. 

In a diabatic representation, the electronic wave functions are no longer eigenfunctions of the electronic Hamiltonian. The aim is instead that the functions are so chosen that the (nonlocal) non-adiabatic coupling operator matrix, A in Eq. (52), vanishes, and the couplings are represented by (local) potential operators. The nuclear Schrddinger equation is then written... 

Until now we have implicitly assumed that our problem is formulated in a space-fixed coordinate system. However, electronic wave functions are naturally expressed in the system bound to the molecule otherwise they generally also depend on the rotational coordinate 4>. (This is not the case for E electronic states, for which the wave functions are invariant with respect to (j> ) The eigenfunctions of the electronic Hamiltonian, v / and v , computed in the framework of the BO approximation ( adiabatic electronic wave functions) for two electronic states into which a spatially degenerate state of linear molecule splits upon bending. 

We write them as i / (9) to shess that now we use the space-fixed coordinate frame. We shall call this basis diabatic, because the functions (26) are not the eigenfunction of the electronic Hamiltonian. The matrix elements of are... 

For vei y small vibronic coupling, the quadratic terms in the power series expansion of the electronic Hamiltonian in normal coordinates (see Appendix E) may be considered to be negligible, and hence the potential energy surface has rotational symmetry but shows no separate minima at the bottom of the moat. In this case, the pair of vibronic levels Aj and A2 in < 3 become degenerate by accident, and the D3/, quantum numbers (vi,V2,/2) may be used to label the vibronic levels of the X3 molecule. When the coupling of the... 

We follow Thompson and Mead [13] to discuss the behavior of the electronic Hamiltonian, potential energy, and derivative coupling between adiabatic states in the vicinity of the D31, conical intersection. Let A be an operator that transforms only the nuclear coordinates, and A be one that acts on the electronic degrees of freedom alone. Clearly, the electronic Hamiltonian satisfies... 

Even w hen we are working solely w ith the electronic Hamiltonian (9-6), w e must remember that the nuclei do move, albeit relatively slowly, with respect to... 

So, for any atom, the orbitals can be labeled by both 1 and m quantum numbers, which play the role that point group labels did for non-linear molecules and X did for linear molecules. Because (i) the kinetic energy operator in the electronic Hamiltonian explicitly contains L2/2mer2, (ii) the Hamiltonian does not contain additional Lz, Lx, or Ly factors. 

One Must be Able to Evaluate the Matrix Elements Among Properly Symmetry Adapted N-Electron Configuration Eunctions for Any Operator, the Electronic Hamiltonian in Particular. The Slater-Condon Rules Provide this Capability... 

For vibrational frequencies, one needs the derivatives of the energy E with respect to deformation of the bond lengths and angles of the molecule, so V is the sum of all changes in the electronic Hamiltonian that arise from displacements 5Ra of the atomic centers... 

For example, the electronic Hamiltonian of atoms, as treated in Chapters 1 and 3 in... 

The implementation of the method using ab initio methods for the quantum region is straightforward. The analogous equations for the electronic Hamiltonian and the corresponding energies in this case are [51]... 

A variety of methodologies have been implemented for the reaction field. The basic equation for the dielectric continuum model is the Poisson-Laplace equation, by which the electrostatic field in a cavity with an arbitrary shape and size is calculated, although some methods do not satisfy the equation. Because the solute s electronic strucmre and the reaction field depend on each other, a nonlinear equation (modified Schrddinger equation) has to be solved in an iterative manner. In practice this is achieved by modifying the electronic Hamiltonian or Fock operator, which is defined through the shape and size of the cavity and the description of the solute s electronic distribution. If one takes a dipole moment approximation for the solute s electronic distribution and a spherical cavity (Onsager s reaction field), the interaction can be derived rather easily and an analytical expression of theFock operator is obtained. However, such an expression is not feasible for an arbitrary electronic distribution in an arbitrary cavity fitted to the molecular shape. In this case the Fock operator is very complicated and has to be prepared by a numerical procedure. 

The physical quantities h, e and all tend to get in the way, so the first task is to write the Hamiltonian in dimensionless form (each variable is now the true variable divided by the appropriate atomic unit). I showed you how to do this in Chapter 0. The electronic Hamiltonian... 

For large molecules, very many terms contribute to the electronic Hamiltonian. To simplify the notation, I am going to collect together all those terms that depend explicitly on the coordinates of a single electron and write them as... 

Using the notation given above for the one- and two-electron operators, the electronic Hamiltonian is... 

So, let s get a bit more chemical and imagine the formation of an H2 molecule from two separated hydrogen atoms, Ha and Hb, initially an infinite distance apart. Electron 1 is associated with nucleus A, electron 2 with nucleus B, and the terms in the electronic Hamiltonian / ab, ba2 and are all negligible when the nuclei are at infinite separation. Thus the electronic Schrodinger equation becomes... 

The first step is to work out e in terms of the one- and two-electron operators and the orbitals. .., For a polyatomic, polyelectron molecule, the electronic Hamiltonian is a sum of terms representing... 

I have grouped the terms on the right-hand side together for a reason. We normally simplify the notation along the lines discussed for dihydrogen in Chapter 4, and write the electronic Hamiltonian as a sum of the one-electron and two-electron operators already discussed. 

Aj[ the beginning of this chapter, I introduced the notion that the 16 electrons iU ethene could be divided conceptually into two sets, the 14 a and the 2 n electrons. Let me refer to the space and spin variables as xi, Xj, > xi6, and for the minute I will formally label electrons 1 and 2 as the 7r-electrons, with 3 through 16 the cr-electrons. Methods such as Huckel rr-electron theory aim to treat the TT-electrons in an effective field due to the nuclei and the remaining a electrons. To see how this might be done, let s look at the electronic Hamiltonian end see if it can be sensibly partitioned into a rr-electron part (electrons 1 and 2) and a cr part (electrons 3 through 16). We have... 

The electronic Hamiltonian commutes with both the square of the angular momentum operator r and its z-component and so the three operators have simultaneous eigenfunctions. Solution of the electronic Schrddinger problem gives the well-known hydrogenic atomic orbitals... 

In the weak-coupling limit unit cell a (, 0 7a for fra/u-polyacetylene) and the Peierls gap has a strong effect only on the electron states close to the Fermi energy eF-0, i.e., stales with wave vectors close to . The interaction of these electronic states with the lattice may then be described by a continuum, model [5, 6]. In this description, the electron Hamiltonian (Eq. (3.3)) takes the form ... 

An important property of the electron Hamiltonian (Eq. (3.3)) is that for arbitrary hopping amplitudes the spectrum of the single-electrons slates is symmetric with respect to c=0 if is the electron amplitude on site n of an eigenstate with energy c, then the state with amplitudes —)"< > is also an eigenstate, with energy -c. In particular, in the uniformly dimerized stale, the gap between the empty conduction and the completely filled valence bands ranges from -A, to A(). 

In the Hamiltonian Eq. (3.39) the first term is the harmonic lattice energy given by Eq. (3.12). It depends only on A iU, i.e., the part of the order parameter that describes the lattice distortions. On the other hand, the electron Hamiltonian Hcl depends on A(.v), which includes the changes of the hopping amplitudes due to both the lattice distortion and the disorder. The free electron part of Hel is given by Eq. (3.10), to which we also add a term Hc 1-1-1 that describes the Coulomb interne-... 

This treatment differs from the usual approach to molecule-radiation interaction through the inclusion of the contribution from the electric field from the beginning and by not treating it as a perturbation to the field free situation. The notation 7/ei(r R, e(f)) makes the parametric dependence of the electronic Hamiltonian on the nuclear coordinates and on the electric field explicit. 

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