Disconnected terms

Model (III) Evaluate properties by Eqn. (26) but with a new A amplitude, which is a solution of the equation without disconnected terms. 

The aldol reaction is extremely important in organic synthesis because it makes compounds with two functional groups in a 1,3-relationship, Whenever you spot this 1,3-relationship in a target molecule—think aldol In disconnection terms we can represent it like this,... 

In this second synthesis of the problematic steroid trans ring junction, the idea is to make the five-membered ring by a Claisen ester condensation and to direct the stereochemistry by tethering the cis groups with a sulfur atom. We can represent this easily in disconnection terms (Chapter 31). The cis-carbons to be joined through sulfur are shown in black. 

Very recently, Mukherjee/91/ made a re-investigation of the problem of the appearance of disconnected terms in H for nh-np determinants as... 

Eq.(5.2.1) indicates that each E has a constant energy shft E. Since f is assumed to be known, the variaiona principles for E and AE (the energy difference) are synonymous. AjE is core-extensive since thee are no disconnected terms containing E. ... 

It may appear that the connectedness of H is not by itself a guarantee for the size-extensivaty of energies, since disconnected terms may appear during the diagonalization. Chaudhuri et al /146/ have demonstrated recently that such is not the case because of the special structure of H... 

The first term generates the reference HF and the second all singly excited states. The first parenthesis generates all doubly excited states, which may be considered as connected (T2) or disconnected (Tj). The second parenthesis generates all triply excited states, which again may be either true (T3) or product triples (T2T1, Tj). The quadruply excited states can similarly be viewed as composed of five terms, a true quadruple and four product terms. Physically a connected type such as T4 corresponds to four electrons interacting simultaneously, while a disconnected term such as T2 corresponds to two... 

Again the terms to be included were based on a perturbation order argument.6,16 The contribution of connected triples was shown numerically to be not inconsequential in applications of perturbation theory.19,20 More recently, Purvis and Bartlett16 reported the equations and initial implementation of a full coupled-cluster singles and doubles model (CCSD) this theory includes all terms in the first five parentheses, C0-C4, of Eq. (6) except for Ti, r4, and T Ti. The inclusion of disconnected terms is known to enhance the numerical stability of the coupled equations.21,22... 

Unlike CID, even CCD introduces quadruple excitations and hextuples etc., up to all -tuples for n electrons. However, the number of coefficients to determine in CCD (iff) is exactly the same as in CID (Cf), because the coefficients of the higher excitations are products of the same coefficients. Since they arise from T l2, T IV., etc., we call the latter disconnected terms (not unlinked all terms in the exaa wavefunction are linked ), which will lead us to a nonlinear set of equations for the determination of the tf. Connected quadruples come from T4. 

The second form uses the commutator to formally eliminate the energy. Before we do that, though, it is apparent that the A equations are Cl-like, as they are energy dependent and are linear. They also retain disconnected terms in their expressions [11,109], since unlike T, A is not composed of solely connected terms. 

Properties computed using Eq. (11) are not size-extensive, however, because of the appearance of unlinked diagrams arising from disconnected terms implicit in Eq. (3). Such terms naturally cancel if the T and operators are not truncated, implying that the EOM-CC method is formally exact in the full-CC limit. 

Comparison of the Biillouin-Wigner coupled cluster theory wth the standard coupled cluster theory. Cancellation of disconnected terms in the Brillouin Wigner coupled cluster theory Czechoslovak Chemical Communications 62, 829 (1997)... 

To obtain an explicit cancelation of the disconnected terms in the Eqs. 3.35 and 3.36 it is necessary to separate those terms out when they appear due the action of the Cl operator, C, on 0). We should note that the use of the semi-linear form of the CASCCSD wave function (3.32) leads to equations which are explicitly dependent on the energy the system, while the fully exponential form of the wave function, (3.12), leads to energy independent equations. We should also add that the CASCC wave function can be alternatively expressed in the following pure linear form ... 

In the next step, we analyze the structure of the various terms generated after the application of the WT to the matrix element in our working equations and establish that we can systematically eliminate the disconnected portion of M, if we keep track of which components of the composites containing F and G are connected. This particular analysis requires the concept of cumulant decomposition [75, 80, 88, 89] of the density matrix elements of Fjt for various ranks k. Since the final working equations are connected after the elimination of the disconnected terms, the cluster amplitudes of F are connected and are compatible with the connectivity of G. ... 

In choosing to deal with G instead of C(11 22 ) and C(11 2), we are able to avoid a rather subtle technical point known as the plateau-value prob-lem. Since there exist disconnected terms that cancel between C(ll 22 ) and jd3 d3 C(ll 3)C (33 )C(3 22 ), it is essential to treat G as a single entity and not deal separately with the two terms in (47). ... 

Since the internal amplitude is by definition zero, the term with denominator and all disconnected terms of the right-hand-side vanish [4,5] and the matrix element is obtained as right-hand-side of the amplitude update equation for s ... 

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