Perturbation theory terms

The second order perturbation theory term with two one-loop self-energy operators does not generate any logarithm squared contribution for the state with nonzero angular momentum since the respective nonrelativistic wave function vanishes at the origin. Only the two-loop vertex in Fig. 3.24 produces a logarithm squared term in this case. The respective perturbation potential determined by the second term in the low-momentum expansion of the two-loop Dirac form factor [111] has the form... 

Formally the contribution of diagram Fig. 7.4 is given by the standard quantum mechanical second order perturbation theory term. Summation over the intermediate states, which accounts for binding, is realized with the help... 

The d(Ej + 2Tvd — E) term clearly identifies this second-order perturbation theory term as a process in which the molecule undergoes a transition from level Et to level. E by absorbing two photons of frequency ox [The second and third terms of Eq. (3.39), surviving when E — Eh represent (elastic) light scattering. The fourth term , surviving when E < Eh represents two-photon stimulated emission.]... 

In a similar way we can show that the probability amplitude for three-photoq absorption, obtained from the third-order perturbation theory term, is given as > ... 

Once both the form of the various perturbation theory terms and the approximations that may be involved in estimating these terms have been validated by comparison with ab-initio MODPOT/... 

The terms on the first line of Eq. (81) describe single and double excitations of the closed core, while those on the second line describe single and double excitations of the atom where the valence orbital is also excited. Substituting Eq. (81) into the Schrodinger equation one obtains a set of coupled equations for the expansion coefficients that can be found in Ref. [44]. The first and second iterations of the equations for the expansion coefficients leads to results that are identical to first- and second-order perturbation theory. In third-order perturbation theory, terms associated with triple excitations contribute to the energy. These terms have no counterpart in the iterative solution to the equations under consideration. 

Another subject with important potential application is discussed in Section XIV. There we suggested employing the curl equations (which any Bohr-Oppenheimer-Huang system has to obey for the for the relevant sub-Hilbert space), instead of ab initio calculations, to derive the non-adiabatic coupling terms [113,114]. Whereas these equations yield an analytic solution for any two-state system (the abelian case) they become much more elaborate due to the nonlinear terms that are unavoidable for any realistic system that contains more than two states (the non-abelian case). The solution of these equations is subject to boundary conditions that can be supplied either by ab initio calculations or perturbation theory. 

Here, Ri f and Rf i are the rates (per moleeule) of transitions for the i ==> f and f ==> i transitions respeetively. As noted above, these rates are proportional to the intensity of the light souree (i.e., the photon intensity) at the resonant frequeney and to the square of a matrix element eonneeting the respeetive states. This matrix element square is oti fp in the former ease and otf ip in the latter. Beeause the perturbation operator whose matrix elements are ai f and af i is Hermitian (this is true through all orders of perturbation theory and for all terms in the long-wavelength expansion), these two quantities are eomplex eonjugates of one another, and, henee ai fp = af ip, from whieh it follows that Ri f = Rf i. This means that the state-to-state absorption and stimulated emission rate eoeffieients (i.e., the rate per moleeule undergoing the transition) are identieal. This result is referred to as the prineiple of microscopic reversibility. 

The effeet of adding in the py orbitals is to polarize the 2s orbital along the y-axis. The amplitudes Cn are determined via the equations of perturbation theory developed below the ehange in the energy of the 2s orbital eaused by the applieation of the field is expressed in terms of the Cn eoeffieients and the (unperturbed) energies of the 2s and npy orbitals. 

The early approaches to this model used perturbative expansion for weak coupling [Silbey and Harris 1983]. Generally speaking, perturbation theory allows one to consider a TLS coupled to an arbitrary bath via the term where / is an operator that acts on the bath variables. The equations of motion in the Heisenberg representation for the a operators, 8c/8t = ih [H, d], have the form... 

Finally, the associative term is computed by using generalizing thermodynamic perturbation theory. One then obtains [38]... 

In perturbation theory, we write the true Hamiltonian H in terms of and a perturbation... 

The spin Hamiltonian operates only on spin wavefunctions, and all details of the electronic wavefunction are absorbed into the coupling constant a. If we treat the Fermi contact term as a perturbation on the wavefunction theR use of standard perturbation theory gives a first-order energy... 

There are three main methods for calculating electron correlation Configuration Interaction (Cl), Many Body Perturbation Theory (MBPT) and Coupled Cluster (CC). A word of caution before we describe these methods in more details. The Slater determinants are composed of spin-MOs, but since the Hamilton operator is independent of spin, the spin dependence can be factored out. Furthermore, to facilitate notation, it is often assumed that the HF determinant is of the RHF type. Finally, many of the expressions below involve double summations over identical sets of functions. To ensure only the unique terms are included, one of the summation indices must be restricted. Alternatively, both indices can be allowed to run over all values, and the overcounting corrected by a factor of 1/2. Various combinations of these assumptions result in final expressions which differ by factors of 1 /2, 1/4 etc. from those given here. In the present book the MOs are always spin-MOs, and conversion of a restricted summation to an unrestricted is always noted explicitly. 

These concepts play an important role in the Hard and Soft Acid and Base (HSAB) principle, which states that hard acids prefer to react with hard bases, and vice versa. By means of Koopmann s theorem (Section 3.4) the hardness is related to the HOMO-LUMO energy difference, i.e. a small gap indicates a soft molecule. From second-order perturbation theory it also follows that a small gap between occupied and unoccupied orbitals will give a large contribution to the polarizability (Section 10.6), i.e. softness is a measure of how easily the electron density can be distorted by external fields, for example those generated by another molecule. In terms of the perturbation equation (15.1), a hard-hard interaction is primarily charge controlled, while a soft-soft interaction is orbital controlled. Both FMO and HSAB theories may be considered as being limiting cases of chemical reactivity described by the Fukui ftinction. 

The reactivity of the carbo-Diels-Alder reaction, as well as the other reactions considered in this chapter, can be accounted for by a simple FMO line of reasoning, i.e., the energy term from second-order perturbation theory... 

The key element in London s approach is the expansion of the electrical potential energy in multipole series. Since neutral molecules or portions of molecules are involved, the leading term is that for dipole-dipole interaction. While attention has been given to higher-order terms, these are usually small, and the greater need seems to be for improved treatment of the dipole-dipole terms. London used second order perturbation theory in his treatment, but Slater and Kirkwood38,21 soon followed with a variation method treatment which yielded similar results. Other individual papers will be mentioned later, but the excellent review of Mar-genau26 should not be overlooked. 

This is an eigenvalue problem of the form of Eq. III.45 referring to the truncated basis only, and the influence of the remainder set is seen by the additional term in the energy matrix. The relation III.48 corresponds to a solution of the secular equation by means of a modified perturbation theory,19 and the problem is complicated by the fact that the extra term in Eq. III.48 contains the energy parameter E, which leads to an iteration procedure. So far no one has investigated the remainder problem in detail, but Eq. III.48 certainly provides a good starting point. 

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