Correlation operators

Wessel, H. E. (1952) Chem. Eng., NY 59 (July) 209. New graph correlates operating labor data for chemical... 

For our purposes, CC theory and its finite order MBPT approximations offer a convenient, compact description of the correlation problem and give rapid convergence to the basis set (i.e. full Cl) limit with different categories of correlation operators (see Fig. 15.1). The coupled-cluster wave function is... 

We have explored whether, on the basis of sound theoretical and physical reasoning, a semiempirical formula can be derived that would directly provide an accurate estimate of the dynamic correlation energy as a whole. Two known rigorous results are suggestive in this context (i) The dynamic correlation energy can be expressed as the expectation value of a perturbing correlation operator (65-67) and (ii) the correlation energy is known to be expressible (10) as sum of contributions of occupied orbital pairs, viz. 

By postulating the correlation operator to be a sum of two-electron operators and assuming the occupied orbitals to be localized, we were able to show that the correlation energy can in fact be approximately expressed in terms of the bilinear expression... 

The term H e is the electron correlation operator, the term H p corresponds to phonon-phonon interaction and H l corresponds to electron-phonon interaction. If we analyze the last term H l we see that when using crude approximation this corresponds to such phonons that force constant in eq. (17) is given as a second derivative of electron-nuclei interaction with respect to normal coordinates. Because we used crude adiabatic approximation in which minimum of the energy is at the point Rg, this is also reflected by basis set used. Therefore this approximation does not properly describes the physical vibrations i.e. if we move the nuclei, electrons are distributed according to the minimum of energy at point Rg and they do not feel correspondingly the R dependence. The perturbation term H) which corresponds to electron-phonon interaction is too large... 

Here in eq. (38) "EpqfpQN a.pag is new Hartree-Fock operator for a new fermions (25), (26), operator Y,pQRsy>pQR a Oq 0s%] is a new fermion correlation operator and Escf is a new fermion Hartree-Fock energy. Our new basis set is obtained by diagonalizing the operator / from eq. (36). The new Fermi vacuum is renormalized Fermi vacuum and new fermions are renormalized electrons. The diagonalization of/ operator (36) leads Jo coupled perturbed Hartree-Fock (CPHF) equations [ 18-20]. Similarly operators br bt) corresponds to renormalized phonons. Using the quasiparticle canonical transformations (25-28) and the Wick theorem the V-E Hamiltonian takes the form... 

Notice that in RS theory the wave operator is the same for all states under investigation. It is convenient to use also another (correlation) operator x, defined by... 

It is possible to express the density fluctuation correlation function by the correlation operator g,2 = Fu - F1F2, and F, may be obtained easily ... 

A general approach to the intramonomer correlation problem is known as the many-electron (or many-body) SAPT method88,141 213-215. In this method the zeroth-order Hamiltonian H0 is decomposed as H0 = F + W, where F = FA + FB is the sum of the Fock operators, FA and FB, of monomer A and B, respectively, and W is the intramonomer correlation operator. The correlation operator can be written as W = WA + WB, where Wx = Hx — Fx, X = A or B. The total Hamiltonian can be now be represented as H = F + V + W. This partitioning of H defines a double perturbation expansion of the wave function and interaction energy. In the SRS theory the wave function is obtained by expanding the parametrized Schrodinger equation as a power series in and A,... 

UMethod originally proposed by H. E. Wessel, New Graph Correlates Operating Labor for Chemical Processes, Chem. Eng., 59(7) 209 (July, 1952). 

The details of SAPT are beyond the scope of the present work. For our purposes it is enough to say that the fundamental components of the interaction energy are ordinarily expanded in terms of two perturbations the intermonomer interaction operator and the intramonomer electron correlation operator. Such a treatment provides us with fundamental components in the form of a double perturbation series, which should be judiciously limited to some low order, which produces a compromise between efficiency and accuracy. The most important corrections for two- and three-body terms in the interaction energy are described in Table 1. The SAPT corrections are directly related to the interaction energy evaluated by the supermolecular approach, Eq.(2), provided that many body perturbation theory (MBPT) is used [19,28]. Assignment of different perturbation and supermolecular energies is shown in Table 1. The power of this approach is its open-ended character. One can thoroughly analyse the role of individual corrections and evaluate them with carefully controlled effort and desired... 

Chalasinski and Szczesniak have provided a means of decomposing the correlation contribution to the interaction energy into four separate terms. Their philosophy takes the electron exchange operator as a second perturbation in the spirit of many-body perturbation theory, with molecular interaction as the first perturbation in their intermolecular Mpller-Plesset perturbation theory (IMPPT). At the level of second order of the correlation operator, they obtain a number of separate terms. The first is the dispersion energy, e... 

This result is easily generalized the normal-ordered form of an operator is simply the operator itself minus its reference expectation value. For the Hamiltonian example, above, the normal-ordered Hamiltonian is just the Hamiltonian minus the SCF energy (i.e., may be considered to be a correlation operator). Owing to its considerable convenience for coupled cluster and many-body perturbation theory analyses, this conventional form of f given in Eq. [105] is adopted for the remainder of this chapter. 

In practical applications of the sapt approach to interactions of many-elect ron systems, one has to use the many-body version of sapt, which includes order-by-order the intramonomer correlation effects. The many-body SAPT is based on the partitioning of the total Hamiltonian as H = F+V+W, where the zeroth-order operator F = Fa + Fb is the sum of the Fock operators for the monomers A and B. The intermolecular interaction operator V = H — Ha — Hb is the difference between the Hamiltonians of interacting and noninteracting systems, and the intramonomer correlation operator W = Wa + Wb is the sum of the Moller-Plesset fluctuation potentials of the monomers Wx — Hx — Fx, X — A or B. The interaction operator V is taken in the non-expanded form, i.e., it is not approximated by the multipole expansion. The interaction energy components of Eq. (1) are now given in the form of a double perturbation series,... 

In practical calculations, one has to expand the nonadditive terms discussed above in powers of intramolecular correlation operator W. Such an expansion was developed in... 

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