Perturbation theory stationary-state

One aspect of the mathematical treatment of the quantum mechanical theory is of particular interest. The wavefunction of the perturbed molecule (i.e. the molecule after the radiation is switched on ) involves a summation over all the stationary states of the unperturbed molecule (i.e. the molecule before the radiation is switched on ). The expression for intensity of the line arising from the transition k —> n involves a product of transition moments, MkrMrn, where r is any one of the stationary states and is often referred to as the third common level in the scattering act. 

Time-dependent response theory concerns the response of a system initially in a stationary state, generally taken to be the ground state, to a perturbation turned on slowly, beginning some time in the distant past. The assumption that the perturbation is turned on slowly, i.e. the adiabatic approximation, enables us to consider the perturbation to be of first order. In TD-DFT the density response dp, i.e. the density change which results from the perturbation dveff, enables direct determination of the excitation energies as the poles of the response function dP (the linear response of the KS density matrix in the basis of the unperturbed molecular orbitals) without formally having to calculate a(co). 

Both the initial- and the final-state wavefunctions are stationary solutions of their respective Hamiltonians. A transition between these states must be effected by a perturbation, an interaction that is not accounted for in these Hamiltonians. In our case this is the electronic interaction between the reactant and the electrode. We assume that this interaction is so small that the transition probability can be calculated from first-order perturbation theory. This limits our treatment to nonadiabatic reactions, which is a severe restriction. At present there is no satisfactory, fully quantum-mechanical theory for adiabatic electrochemical electron-transfer reactions. 

The interest aroused by the field of radiationless transitions in recent years has been enormous, and several reviews have been published 72-74) Basically, the ideas of Robinson and Frosch 75) who used the concepts on non-stationary molecular states and time-dependent perturbation theory to calculate the rate of transitions between Born-Oppenheimer states, are still valid, although they have been extended and refined. The nuclear kinetic energy leads to an interaction between different Born-Oppenheimer states and the rate of radiationless transitions is given by... 

Bardeen considers two separate subsystems first. The electronic states of the separated subsystems are obtained by solving the stationary Schrodinger equations. For many practical systems, those solutions are known. The rate of transferring an electron from one electrode to another is calculated using time-dependent perturbation theory. As a result, Bardeen showed that the amplitude of electron transfer, or the tunneling matrix element M, is determined by the overlap of the surface wavefunctions of the two subsystems at a separation surface (the choice of the separation surface does not affect the results appreciably). In other words, Bardeen showed that the tunneling matrix element M is determined by a surface integral on a separation surface between the two electrodes, z = zo. 

The polarization, or the van der Waals interaction, can be accounted for by a stationary-state perturbation theory, effectively and accurately. The exchange interaction or tunneling can be treated by time-dependent perturbation theory, following the method of Oppenheimer (1928) and Bardeen (1960). In this regime, the polarization interaction is still in effect. Therefore, to make an accurate description of the tunneling effect, both perturbations must be considered simultaneously. This is the essence of the MBA. 

There is another way of looking at this coupled ion system, namely, in terms of stationary states. From this point of view, one considers that the excitation belongs to both ions simultaneously. To determine the wave functions of the two-ion system, one resorts to degenerate perturbation theory. The coupling H can be shown to remove the degeneracy, and two new states that are mixtures of X20 and X11 are formed. For each the excita-... 

The semiclassical treatment just given has the defect of not predicting spontaneous emission. According to (3.13), if there is no outside perturbation, that is, if // (0 = 0, then dcm/dt = 0 for all m if the atom is in the nth stationary state at / = 0, it will persist in that state forever. However, experimentally we find that unperturbed atoms in excited states spontaneously radiate energy and drop to lower states. Quantum field theory does predict spontaneous emission. Since quantum field theory is beyond us, we shall use an argument given by Einstein in 1917 to find the spontaneous-emission probability. 

In the previous chapter we have briefly discussed the use of the stationary many-body perturbation theory of the effective Hamiltonian, sketched in Chapter 3, to account for correlation effects. Here we shall continue such studies for electronic transitions on the example of the oxygen isoelectronic sequence. Having in mind (29.32) and the approximation Q(1) iiji the matrix element of the 1-transition operator Oei between the initial state... 

A modified effective Hamiltonian Goep is defined by replacing vxc by a model local potential vxc(r). The energy functional is made stationary with respect to variations of occupied orbitals that are determined by modified OEL equations in which Q is replaced by Goep- 84>i is determined by variations 8vxc(r) in these modified OEL equations. To maintain orthonormality, <5, can be constrained to be orthogonal to all occupied orbitals of the OEP trial state , so that (r) = J]a(l — na)i). First-order perturbation theory for the OEP Euler-Lagrange equations implies that... 

Spectroscopy is concerned with the observation of transitions between stationary states of a system, with the accompanying absorption or emission of electromagnetic radiation. In this section we consider the theory of transition probabilities, using time-dependent perturbation theory, and the selection rules for transitions, particularly those relevant for rotational spectroscopy. 

A review of the semidassical method is given by Cottrell and McCoubrey [9] and by Rapp and Kassal [13]. In this method, the translational motion is treated classically, while the molecule BC is assumed to have quantized vibrational levels. By converting the force V (x) on the oscillator due to the incident atom to V (t) by utilization of the classical trajectory x(t), one may apply time dependent perturbation theory. The wave function for the perturbed system is written as a sum of the stationary-state wave functions Y (y)exp( —icojf), with coefficients ck given by... 

The application of this model in physics and chemistry has had a long history. We shall give some examples of the early works. The work of Einstein S2) on the theory of Brownian motion is based on a random walk process. Dirac S3) used the model to discuss the time behavior of a quantum mechanical ensemble under the influence of perturbations this development enables one to discuss the probability of transition of a system from one unperturbed stationary state to another. Pauli 34) [also see Tolman 35)], in his treatment of the quantum mechanical H-theorem, is concerned with the approach to equilibrium of an assembly of quantum states. His equations are identical with those of a general monomolecular... 

For very small field amplitudes, the multiphoton resonances can be treated by time-dependent perturbation theory combined with the rotating wave approximation (RWA) [10]. In a strong field, all types of resonances can be treated by the concept of the rotating wave transformation, combined with an additional stationary perturbation theory (such as the KAM techniques explained above). It will allow us to construct an effective Hamiltonian in a subspace spanned by the resonant dressed states, degenerate at zero field. 

The computationally viable description of electron correlation for stationary state molecular systems has been the subject of considerable research in the past two decades. A recent review1 gives a historical perspective on the developments in the field of quantum chemistry. The predominant methods for the description of electron correlation have been configuration interactions (Cl) and perturbation theory (PT) more recently, the variant of Cl involving reoptimization of the molecular orbitals [i.e., multiconfiguration self-consistent field (MCSCF)] has received much attention.1 As is reasonable to expect, neither Cl nor PT is wholly satisfactory a possible alternative is the use of cluster operators, in the electron excitations, to describe the correlation.2-3... 

Spectroscopic studies of the Stark effect lead, through application of quantum-mechanical perturbation theory, to values for the dipole moments of molecules in particular stationary states.4 Very careful work, such as the microwave Stark studies of Scharpen, Muenter, and Laurie5 on OCS, NNO, and CD3 —C=C—H, and the molecular beam elec-... 

The stability of the uniform stationary states in system (3,4) to small spatially uniform perturbations (SUPs) was studied in detail by the theory of perfectly stirred reactors (see reference 9). It will be recalled that the system... 

The QTS is a part of a reaction mechanism. These species may be found related to stationary arrangements of the external Coulomb sources. Solutions to eq.(8) coming as saddle points of at least index one (one imaginary frequency) are natural candidates to play the role of QTS. If the saddle point wave function has closed electronic shell structure, its electronic parity is positive. In this case one would expect a situation similar to the symmetry-forbidden electronic absorption bands. The intensity is borrowed from the excited states having the correct parity via couplings at second-order perturbation theory [21]. 

There have been developed two essentially different wave-mechanical perturbation theories. The first of these, due to Schrodinger, provides an approximate method of calculating energy values and wave functions for the stationary states of a system under the influence of a constant (time-independent) perturbation. We have discussed this theory in Chapter VI. The second perturbation theory, which we shall-treat in the following paragraphs, deals with the time behavior of a system under the influence of a perturbation it permits us to discuss such questions as the probability of transition of the system from one unperturbed stationary state to another as the result of the perturbation. (In Section 40 we shall apply the theory to the problem of the emission and absorption of radiation.) The theory was developed by Dirac.1 It is often called the theory of the variation of constants the reason for this name will be evident from the following discussion. 

The interaction energy between an electron moving with velocity v a)id an electromagnetic radiation Held described by die vector potential At , t) is (non-relati vistically) —ev. A(r, t). In first-order perturbation theory this interaction energy vanishes for a stationary state since it is periodic in the time, and the diagonal matrix elements vanish. The non-diagonal matrix elements, however, do not vanish, so that there is a non vanishing second-order perturbation for the state m whose value is... 

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