Electron correlation methods size extensivity

In a nutshell (electron correlated methods) Complete electronic description, straightforward interpretation Highly accurate methods that can rival experiment for small organic molecules Very time consuming Cl methods are not size-extensive CC methods are non-variational Slow convergence Strongly basis set dependent Systematic improvement straightforward. 

The coupled cluster (CC) approach is the most powerful and accurate of generally applicable electron correlation methods. This has been shown in many benchmark applications of 4-component relativistic CC methods to atoms [11-18] and molecules [19-31]. The CC method is an all-order, size-extensive, and systematic many-body approach. Multireference variants of relativistic 4-component CC methods capable of handling quasidegeneracies, which are important for open-shell heavy atomic and molecular systems, have been developed in recent years [15,17-19,21,31]. In particular, the multireference FSCC scheme [32,33] is applicable to systems with a variable number of particles, and is an ideal candidate for merging with QED theory to create an infinite-order size-extensive covariant many-body method applicable to systems with variable numbers of fermions and bosons [6,7]. 

Size-extensivity is of importance when one wishes to compare several similar systems with different numbers of atoms (i.e., methanol, ethanol, etc.). In all cases, the amount of correlation energy will increase as the number of atoms increases. However, methods that are not size-extensive will give less correlation energy for the larger system when considered in proportion to the number of electrons. Size-extensive methods should be used in order to compare the results of calculations on different-size systems. Methods can be approximately size-extensive. The size-extensivity and size-consistency of various methods are summarized in Table 26.1. 

The inclusion of electron correlation is generally necessary to get reliable results. However, the use of methods that extensively include electron correlation is limited by the computational cost associated with the size of the systems. 

It has been found repeatedly [1, 43, 45] that scalar relativistic contributions are overestimated by about 20 - 25 % in absolute value at the SCF level. Hence inclusion of electron correlation is essential we found the ACPF method (which is both variational and approximately size extensive) to be an excellent compromise between quality and cost. It is reasonable to suppose that for a property that becomes more important as one approaches the nucleus, one wants maximum flexibility of the wavefunction near the nucleus as well as correlation of all electrons thus we finally opted for ACPF/MTsmall as our approach of choice. Typically the cost of the scalar relativistic step is a fairly small fraction of that of the core correlation step, since only n2N4 scaling is involved in the ACPF calculations. 

The electron correlation problem remains a central research area for quantum chemists, as its solution would provide the exact energies for arbitrary systems. Today there exist many procedures for calculating the electron correlation energy (/), none of which, unfortunately, is both robust and computationally inexpensive. Configuration interaction (Cl) methods provide a conceptually simple route to correlation energies and a full Cl calculation will provide exact energies but only at prohibitive computational cost as it scales factorially with the number of basis functions, N. Truncated Cl methods such as CISD (A cost) are more computationally feasible but can still only be used for small systems and are neither size consistent nor size extensive. Coupled cluster... 

For the treatment of electron correlation, Cizek uses classical techniques as well as techniques based on mathematical methods of quantum field theory, namely, a coupled-cluster approach. A rapid development and deployment of these methods during the past decade was stimulated by the realization of the importance of size consistency or size extensivity in the studies of reactive chemical processes. Although truly remarkable accuracy and development have been achieved for ground states of closed-shell systems, an extension to quasidegenerate and general open-shell systems is most challenging. Cizek also works on the exploitation of these approaches to study the electronic structure of extended systems (molecular crystals, polymers107). His many interests in-... 

The CASSCF method itself is not very useful for anything else than systems with few electrons unless an effective method to treat dynamical correlation effects could be developed. The Multi-Reference Cl (MRCI) method was available but was limited due to the steep increase of the size of the Cl expansion as a function of the number of correlated electrons, the basis set, and the number of active orbitals in the reference function. The direct MRCI formulation by P. Siegbahn helped but the limits still prevented applications to larger systems with many valence electrons [20], The method is still used with some success due to recent technological developments [21], Another drawback with the MRCI approach is the lack of size-extensivity, even if methods are available that can approximately correct the energies. Multi-reference coupled-cluster methods are studied but have not yet reached a state where real applications are possible. 

UHF case when electron correlation is introduced. The main problem with the UHF method is the spin contamination, and there have truncated Cl are not. The lack of size extensivity is the reason why CISD recovers less and less electron correlation as the systems grow larger. 

The relative importance of electronic and vibrational effects has been a prominent topic in recent years, but reliable calculations of the vibrational contributions to the hyperpolarizabilities can only be achieved by using correlated methods with fairly large basis sets and time consuming computational procedures. The extension of such computations to medium sized organic... 

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