Schrodinger equation excitation

The discussion in the previous sections assumed that the electron dynamics is adiabatic, i.e. the electronic wavefiinction follows the nuclear dynamics and at every nuclear configuration only the lowest energy (or more generally, for excited states, a single) electronic wavefiinction is relevant. This is the Bom-Oppenlieimer approxunation which allows the separation of nuclear and electronic coordinates in the Schrodinger equation. 

Using the variational Cl energies and correcting these for higher order excitations, the radial Schrodinger equation solutions for E(ZP) are equal to 712.1cm and 667.4cm respectively with rmin=1.417lAand Tmax=2.93A. 

The development of an ab initio quantum molecular dynamics method is guided by the need to overcome two main obstacles. First, one needs to develop an efficient, yet accurate, method for solving the electronic Schrodinger equation for both ground and excited electronic states. Second, the quantum mechanical character of the nuclear dynamics must be addressed. (This is necessary for the description of photochemical and tunneling processes.) This section provides a detailed discussion of the approaches we have taken to solve these two problems. 

Interaction with light changes the quantum state a molecule is in, and in photochemistry this is an electronic excitation. As a result, the system will no longer be in an eigenstate of the Hamiltonian and this nonstationary state evolves, governed by the time-dependent Schrodinger equation... 

Now, consider the general case of a V2 multiply excited degenerate vibrational level where V2 > 2, which is dealt with by solving the Schrodinger equation for the isotropic 2D harmonic oscillator with the Hamiltonian... 

The difference between the Hartree-Fock energy and the exact solution of the Schrodinger equation (Figure 60), the so-called correlation energy, can be calculated approximately within the Hartree-Fock theory by the configuration interaction method (Cl) or by a perturbation theoretical approach (Mpller-Plesset perturbation calculation wth order, MPn). Within a Cl calculation the wave function is composed of a linear combination of different Slater determinants. Excited-state Slater determinants are then generated by exciting electrons from the filled SCF orbitals to the virtual ones ... 

Even for a diatomic molecule the nuclear Schrodinger equation is generally so complicated that it can only be solved numerically. However, often one is not interested in all the solutions but only in the ground state and a few of the lower excited states. In this case the harmonic approximation can be employed. For this purpose the potential energy function is expanded into a Taylor series about the equilibrium separation, and terms up to second order are kept. For a diatomic molecule this results in ... 

The study of behavior of many-electron systems such as atoms, molecules, and solids under the action of time-dependent (TD) external fields, which includes interaction with radiation, has been an important area of research. In the linear response regime, where one considers the external held to cause a small perturbation to the initial ground state of the system, one can obtain many important physical quantities such as polarizabilities, dielectric functions, excitation energies, photoabsorption spectra, van der Waals coefficients, etc. In many situations, for example, in the case of interaction of many-electron systems with strong laser held, however, it is necessary to go beyond linear response for investigation of the properties. Since a full theoretical description based on accurate solution of TD Schrodinger equation is not yet within the reach of computational capabilities, new methods which can efficiently handle the TD many-electron correlations need to be explored, and time-dependent density functional theory (TDDFT) is one such valuable approach. 

Consequently, from the density the Hamiltonian can be readily obtained, and then every property of the system can be determined by solving the Schrodinger equation to obtain the wave function. One has to emphasize, however, that this argument holds only for Coulomb systems. By contrast, the density functional theory formulated by Hohenberg and Kohn is valid for any external potential. Kato s theorem is valid not only for the ground state but also for the excited states. Consequently, if the density n, of the f-th excited state is known, the Hamiltonian H is also known in principle and its eigenvalue problem ... 

With the triples correction added, the error relative to experiment is still as large as 15 kJ/mol. More importantly, we are now above experiment and it is reasonable to assume that the inclusion of higher-order excitations (in particular quadruples) would increase this discrepancy even further, perhaps by a few kJ/mol (judging from the differences between the doubles and triples corrections). Extending the coupled-cluster expansion to infinite order, we would eventually reach the exact solution to the nonrelativistic clamped-nuclei electronic Schrodinger equation, with an error of a little more than 15 kJ/mol. Clearly, for agreement with experiment, we must also take into account the effects of nuclear motion and relativity. 

The theoretical approach is based on the solution to the mixed type linear/nonlinear generalized Schrodinger equation for spatiotemporal envelope of electrical field with account of transverse spatial derivatives and the transverse profile of refractive index. In the quasi-static approximation, this equation is reduced to the linear/nonlinear Schrodinger equation for spatiotemporal pulse envelope with temporal coordinate given as a parameter. Then the excitation problem can be formulated for a set of stationary light beams with initial amplitude distribution corresponding to temporal envelope of the initial pulse. 

On the other hand, by substituting Eq. (14) in the Schrodinger equation and projecting it onto single and double excitations, we get. 

An important consequence of the equivalence of the 2-CSE and higher-order CSEs with the Schrodinger equation is that the CSEs may be applied to the study not only of the ground-state but also of excited states. 

---