Born Oppenheimer approximation electric field

Equation (28) is the set of exact coupled differential equations that must be solved for the nuclear wave functions in the presence of the time-varying electric field. In the spirit of the Born-Oppenheimer approximation, the ENBO approximation assumes that the electronic wave functions can respond immediately to changes in the nuclear geometry and to changes in the electric field and that we can consequently ignore the coupling terms containing... 

We wanted to extend this approach to include dynamical effects on line shapes. As discussed earlier, for this approach one needs a trajectory co t) for the transition frequency for a single chromophore. One could extract a water cluster around the HOD molecule at every time step in an MD simulation and then perform an ab initio calculation, but this would entail millions of such calculations, which is not feasible. Within the Born Oppenheimer approximation the OH stretch potential is a functional of the nuclear coordinates of all the bath atoms, as is the OH transition frequency. Of course we do not know the functional. Suppose that the transition frequency is (approximately) a function of a one or more collective coordinates of these nuclear positions. A priori we do not know which collective coordinates to choose, or what the function is. We explored several such possibilities, and one collective coordinate that worked reasonably well was simply the electric field from all the bath atoms (assuming the point charges as assigned in the simulation potential) on the H atom of the HOD molecule, in the direction of the OH bond. 

In this chapter we describe the various stages of the factorisation process. Following the separation of translational motion by reference of the particles coordinates to the molecular centre of mass, we separate off the rotational motion by referring coordinates to an axis system which rotates with the molecule (the so-called molecule-fixed axis system). Finally, we separate off the electronic motion to the best of our ability by invoking the Born-Oppenheimer approximation when the electronic wave function is obtained on the assumption that the nuclei are at a fixed separation R. Some empirical discussion of the involvement of electron spin, in either Hund s case (a) or (b), is also included. In conclusion we consider how the effects of external electric or magnetic fields are modified by the various transformations. 

The difference equation or numerical integration method for vibrational wavefunctions usually referred to as the Numerov-Cooley method [111] has been extended by Dykstra and Malik [116] to an open-ended method for the analytical differentiation of the vibrational Schrodinger equation of a diatomic. This is particularly important for high-order derivatives (i.e., hyperpolarizabilities) where numerical difficulties may limit the use of finite-field treatments. As in Numerov-Cooley, this is a procedure that invokes the Born-Oppenheimer approximation. The accuracy of the results are limited only by the quality of the electronic wavefunction s description of the stretching potential and of the electrical property functions and by the adequacy of the Born-Oppenheimer approximation. 

Derivatives of the dipole moment with respect to Qj can be expressed within a Cartesian reference frame via a similarity transformation, introducing atomic polar tensors (APTs) [13, 14], The connection between the latter and the electric shielding is obtained by means of the Hellmann-Feynman theorem. Within the Born-Oppenheimer approximation and allowing for the dipole length formalism, the perturbed Hamiltonian in the presence of a static external electric field E is given by Eqs. (6) and (35). 

For homonuclear molecules, the g or u symmetry is almost always conserved. Only external electric fields, hyperfine effects (Pique, et al., 1984), and collisions can induce perturbations between g and u states. See Reinhold, et al., (1998) who discuss how several terms that are neglected in the Born-Oppenheimer approximation can give rise to interactions between g and u states in hetero-isotopomers, as in the HD molecule. An additional symmetry will be discussed in Section 3.2.2 parity or, more usefully, the e and / symmetry character of the rotational levels remains well defined for both hetero- and homonuclear diatomic molecules. The matrix elements of Table 3.2 describe direct interactions between basis states. Indirect interactions can also occur and are discussed in Sections 4.2, 4.4.2 and 4.5.1. Even for indirect interactions the A J = 0 and e / perturbation selection rules remain valid (see Section 3.2.2). 

Solid State Physical Methods. - The theoretical treatment of a molecule or a polymer in the presence of an electric field or more generally of a laser beam presents a formidable problem. Here we shall remain first within the framework of the Born-Oppenheimer approximation and shall not consider the change of the phonons in the presence of an electric field because we shall work in a fixed nuclear (framework). Further, first we shall not take into account the effect of the interaction between the linear polymers on their polarizabilities and hyperpolarizabilities either although both effects are non-neglible.110-1,2 They will be treated subsequently. 

Vext is an external static electric or magnetic field. For Ham we will assume the Born-Oppenheimer approximation, which allows the decoupling of the motion of electrons from those of the nuclei. 

The above calculation represents an example of the application to an atom of what is called the finite field method. In this method we solve the Schrodinger equation for the system in a given homogeneous (weak) electric field. Say, we are interested in the approximate values of Uqq/ for a molecule. First, we choose a coordinate system, fix the positions of the nuelei in space (the Born-Oppenheimer approximation) and ealeulate the number of electrons in the molecule. These are the data needed for the input into the reliable method we choose to calculate E S). Then, using eqs. (12.38) and (12.24) we calculate the permanent dipole moment, the dipole polarizability, the dipole hyperpolarizabilities, etc. by approximating E(S) by a power series of Sq A. 

In the previous sections, the Born-Oppenheimer approximation was assumed, i.e. nuclear motion on a single PES was considered. However, in many simations, the dynamics of the nuclei need to be treated on several PESs corresponding to coupled electronic state. The coupling between the electronic states can be due to the presence of an external electric field or to internal vibronic interactions. There exists two different ways of treating several coupled electronic states with the MCTDH method [60], the single-set formulation and the multi-set formulation. 

The ]V-electron operators p. Ro) and Q Ro) will in the following often be called the electric dipole operator and the electric quadrupole operator, respectively. Although we are working within the Born-Oppenheimer approximation we have included the interaction of the electric field and field gradient with the nuclear charges in the molecular Hamiltonian in Eq. (2.101). This interaction then leads to nuclear contributions to the perturbation Hamiltonian operators. The operators and... 

Yaspatial positions rj of the N molecules yields a set of energy eigenvalues ( rj ), which can be interpreted as the effective Al-particle potential in the single-channel many-body Hamiltonian (Equation 12.1). The dependence of Vgl ( r ) on the electric fields E provides the basis for the engineering of the many body interactions in (Equation 12.2). The validity of this adiabatic approximation and of the associated decoupling of the Born-Oppenheimer channels will be discussed below. 

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