Schrodinger equation motions

I i i(q,01 in configuration space, e.g. as defined by the possible values of the position coordinates q. This motion is given by the time evolution of the wave fiinction i(q,t), defined as die projection ( q r(t)) of the time-dependent quantum state i i(t)) on configuration space. Since the quantum state is a complete description of the system, the wave packet defining the probability density can be viewed as the quantum mechanical counterpart of the classical distribution F(q- i t), p - P t)). The time dependence is obtained by solution of the time-dependent Schrodinger equation... 

Let us define x (R>.) as an n-dimensional nuclear motion column vector, whose components are Xi (R i) through X (R )- The n-electronic-state nuclear motion Schrodinger equation satisfied by (Rl) can be obtained by inserting Eqs. (12)... 

This makes it desirable to define other representations in addition to the electronically adiabatic one [Eqs. (9)-(12)], in which the adiabatic electronic wave function basis set used in the Bom-Huang expansion (12) is replaced by another basis set of functions of the electronic coordinates. Such a different electronic basis set can be chosen so as to minimize the above mentioned gradient term. This term can initially be neglected in the solution of the / -electionic-state nuclear motion Schrodinger equation and reintroduced later using perturbative or other methods, if desired. This new basis set of electronic wave functions can also be made to depend parametrically, like their adiabatic counterparts, on the internal nuclear coordinates q that were defined after Eq. (8). This new electronic basis set is henceforth refened to as diabatic and, as is obvious, leads to an electronically diabatic representation that is not unique unlike the adiabatic one, which is unique by definition. 

U(qJ is referred to as an adiabatic-to-diabatic transformation (ADT) matrix. Its mathematical sbucture is discussed in detail in Section in.C. If the electronic wave functions in the adiabatic and diabatic representations are chosen to be real, as is normally the case, U(q ) is orthogonal and therefore has n n — l)/2 independent elements (or degrees of freedom). This transformation mabix U(qO can be chosen so as to yield a diabatic electronic basis set with desired properties, which can then be used to derive the diabatic nuclear motion Schrodinger equation. By using Eqs. (27) and (28) and the orthonormality of the diabatic and adiabatic electronic basis sets, we can relate the adiabatic and diabatic nuclear wave functions through the same n-dimensional unitary transformation matrix U(qx) according to... 

This can be used to rewrite the diabatic nuclear motion Schrodinger equation for an incomplete set of n electronic states as... 

In the two-adiabatic-electronic-state Bom-Huang description of the total orbital wave function, we wish to solve the corresponding nuclear motion Schrodinger equation in the diabatic representation... 

The familiar BO approximation is obtained by ignoring the operators A completely. This results in the picture of the nuclei moving over the PES provided by the electrons, which are moving so as to instantaneously follow the nuclear motion. Another common level of approximation is to exclude the off-diagonal elements of this operator matrix. This is known as the Bom-Huang, or simply the adiabatic, approximation (see [250] for further details of the possible approximations and nomenclature associated with the nuclear Schrodinger equation). 

We will study the equations of motion that result from inserting all this in the full Schrodinger equation, Eq. (1). However, we would like to remind the reader that not the derivation of these equations of motion is the main topic here but the question of the quality of the underlying approximations. 

It was stated above that the Schrodinger equation cannot be solved exactly for any molecular systems. However, it is possible to solve the equation exactly for the simplest molecular species, Hj (and isotopically equivalent species such as ITD" ), when the motion of the electrons is decoupled from the motion of the nuclei in accordance with the Bom-Oppenheimer approximation. The masses of the nuclei are much greater than the masses of the electrons (the resting mass of the lightest nucleus, the proton, is 1836 times heavier than the resting mass of the electron). This means that the electrons can adjust almost instantaneously to any changes in the positions of the nuclei. The electronic wavefunction thus depends only on the positions of the nuclei and not on their momenta. Under the Bom-Oppenheimer approximation the total wavefunction for the molecule can be written in the following form ... 

Whereas the tight-binding approximation works well for certain types of solid, for other s. items it is often more useful to consider the valence electrons as free particles whose motion is modulated by the presence of the lattice. Our starting point here is the Schrodinger equation for a free particle in a one-dimensional, infinitely large box ... 

For translational, rotational and vibrational motion the partition function Ccin be calculated using standard results obtained by solving the Schrodinger equation ... 

Beeause there are no terms in this equation that couple motion in the x and y directions (e.g., no terms of the form x yb or 3/3x 3/3y or x3/3y), separation of variables can be used to write / as a product /(x,y)=A(x)B(y). Substitution of this form into the Schrodinger equation, followed by collecting together all x-dependent and all y-dependent terms, gives ... 

This Schrodinger equation relates to the rotation of diatomic and linear polyatomic molecules. It also arises when treating the angular motions of electrons in any spherically symmetric potential... 

This Schrodinger equation forms the basis for our thinking about bond stretching and angle bending vibrations as well as collective phonon motions in solids... 

The Application of the Schrodinger Equation to the Motions of Electrons and Nuclei in a Molecule Lead to the Chemists Picture of Electronic Energy Surfaces on Which Vibration and Rotation Occurs and Among Which Transitions Take Place. 

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