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From Configuration Interaction to Coupled Cluster Theory: the Quadratic Configuration Interaction Approach Dieter Cremer*

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From Configuration Interaction to Coupled Cluster Theory: the Quadratic Configuration Interaction Approach Dieter Cremer* Advanced Review From configuration interaction to coupled cluster theory: The quadratic configuration interaction approach Dieter Cremer* Configuration interaction (CI) theory has dominated the first 50 years of quantum chemistry before it was replaced by many-body perturbation theory and coupled cluster theory. However, even today it plays an important role in the education of everybody who wants to enter the realm of quantum chemistry. Apart from this, full CI is the method of choice for getting exact energies for a given basis set. The development of CI theory from the early days of quantum chemistry up to our time is described with special emphasis on the size-extensivity problem, which after its discovery has reduced the use of CI methods considerably. It led to the development of the quadratic CI (QCI) approach as a special form of size- extensive Cl. Intimately linked with QCI is the scientific dispute between QCI developers and their opponents, who argued that the QCI approach in its original form does not lead to a set of size-extensive CI methods. This dispute was settled when it was shown that QCI in its original form can be converted into a generally defined series of size-extensive methods, which however have to be viewed as a series of simplified coupled cluster methods rather than a series of size-extensive CI methods. © 2013 John Wiley & Sons, Ltd. How to cite this article: WIREs Comput Mol Sci 2013, 3:482-503 doi: 10.1002/wcms.1131 INTRODUCTION AND BASIC TERMS Theory edited by Schaefer. In the same book, Roos 2 3 onfiguration interaction (CI) theory was the and Siegbahn and Meyer reported on related devel- first post-HF (Hartree-Fock) [also called post- opments in CI theory thus complementing Shavitt's C 4 SCF (self-consistent field)] method used in the early review. In 1998, Carsky summarized in an excellent days of quantum chemistry to correct the mean-field review developments during 70 years of CI theory approach (MFA) of HF for a better description of and 1 year later Sherill and Schaefer gave a detailed 5 electron-electron interactions. In the early literature, account on highly correlated CI theory. one used the term superposition of configurations, Since CI theory has played such a fundamental which as an acronym would be misleading nowadays role in the development, understanding, and applica- because it denotes spin orbit coupling. Therefore, we tion of electron correlation methods, it is discussed in will avoid the latter term in this article. literally all textbooks on quantum chemistry of which 6 A number of review articles have focused on only the book by Szabo and Ostlund is mentioned CI theory. A state-of-the-art account was given by here. In the following, some basic terms will be intro- Shavitt1 in 1977 in Methods of Electronic Structure duced that facilitate the reading of this review. HF theory simplifies the description of the in- teractions of N electrons by considering just one *Correspondence to: [email protected] electron interacting with the mean field of the N - Computational and Theoretical Chemistry Group (CATCO), De- partment of Chemistry, Southern Methodist University, Dallas, 1 remaining electrons thus reducing the many-body TX,USA (many-electron) problem to an effective one-body DOl: 10.1002/wcms.1131 (one-electron) problem. This is the essence of the 482 © 2013 John Wiley & Sons, Ltd. Volume 3, September/October 2013 WIREs Computational Molecular Science Configuration interaction and quadratic configuration interaction MFA, which implies a drastic simplification of the cal meaning from the electron attachment process.8 description of electron-electron interactions. The HF (ii) The nodal properties of the virtual HF orbitals space orbitals ¢i or spin orbitals lj!i (subscripts i, j, k, (with increasing orbital energies, the number of nodal 1, ... denote orbitals with occupation numbers ni = surfaces of the virtual orbitals increases) can be ex- 2, 1, or 0 in the case of space orbitals or ni = 1 or 0 in ploited to improve the HF description of the electron the case of spin orbitals) are calculated variationally interaction. For this purpose, excited configurations as a linear combination of M basis functions x 11 : are generated by moving electrons from occupied to M virtual orbitals (denoted by subscripts a, b, c, etc.; ¢i = L C11 iX11 with fL = 1, 2, ... , M (1) for orbitals with unspecified electron occupation sub- f1 scripts p, q, r, s, etc., are used). In the case of the wa- where the expansion coefficients c11 i are variationally ter molecule, doubly (D) excited configurations are optimized. Hence, the HF energy E(HF) based on for example: (2222011000000), (2222020000000), these orbitals is an upper bound to the exact energy or (2222002000000). The virtual orbitals possess ad- E(exact). The difference between the exact, nonrela- ditional nodal surfaces, which separate two electrons, tivistic Schrodinger energy (obtained for a clamped and therefore a better description of the correlated nuclei situation, i.e., with the Born-Oppenheimer ap- movements of the electrons is achieved. Depending proximation) and the HF limit energy (obtained for a on the nodal properties of originally and newly oc- 7 complete basis set) is called correlation energy : cupied orbital, one speaks of in-out (ns --+ ks with k > n, etc.), angular (a --+ n*), or left-right (a --+ l'lE(corr) = E(exact)- E(HF, limit) (2) a*) excitations, which describe in-out, angular, and It accounts for the energy lowering due to a corre- left-right electron correlation, respectively. The corre- lated movement of the electrons in a many-electron sponding Slater determinants are written in the short molecule thus reducing the destabilizing electron in- form l<t>fl), which indicates that the occupied orbitals teractions and correcting in this way the MFA of HF. ¢i and ¢i as well as the virtual orbitals ¢a and ¢b Since HF is carried out with a finite set of M basis are involved in the excitation process. In this way, a functions, the correlation energy depends on the size CID (CI with all D excitations) wavefunction can be of the basis set. It also depends on how the HF method generated: is improved. This can be done in a methodologically a>b 1 simple way by employing CI theory. l\llcw) = coi<I>o) + l..:cfll<t>fl) (3) A set of occupation numbers (nt, n2, n3, .. , nM) i>j is called an electron configuration. When using space orbitals and describing a closed shell molecule in its where co is the coefficient of the HF reference, which ground state, m = N/2 orbitals with the lowest ener- can be one or close to one depending on what normal- gies are doubly occupied. For example, in the case of a ization is used. The cfl are the mixing(= interaction) VDZ (valence double-zeta) basis set description of the coefficients of the excited configurations. Hence, the water molecule (N = 10, M = 13), the ground state CID wavefunction is expressed as a linear combina- (GS) configuration is given by the occupation vector tion of the HF Slater determinant and all possible (2222200000000) because there are five doubly oc- D-excited Slater determinants, which can be gener- cupied (ni = 2) molecular (space) orbitals (MOs) and ated for a set of 13 MOs and 10 electrons. The CID eight virtual orbitals with na = 0 (subscripts i and weighting coefficients cfl are determined by a varia- a denote occupied and virtual orbitals, respectively). tional approach during which the HF orbitals are kept The corresponding wavefunction is the HF Slater de- frozen. The resulting CID energy is lower than the HF terminant I<Po) derived from the space orbitals, which energy, however still an upper bound to E(exact). The are expanded by the functions of the VDZ basis set. It difference l'lE(corr, CID) = E(CID) - E(HF) is the has to be noted that the ket vector I ) is used to denote CID correlation energy, which accounts for electron the quantum state described by the wavefunction in pair correlation effects of the in-out, angular, and left- question. right type. Although the virtual orbitals of a HF calculation In the following, we will express the CI method- have no direct physical meaning (they are by-products ology in terms of spin orbitals 1jJ i because this is some- of a HF calculation), they can be used in two differ- what simpler than working with space orbitals ¢i· ent ways: (i) They approximate the Dyson orbitals In general, the functions of a CI expansion such as (constructed from Feynman-Dyson amplitudes) and Eq. (3) are chosen to be eigenfunctions of the spin 2 their orbital energies the exact electron affinities. In operators Sz and S , which commute with the Hamil- this way, the virtual HF orbitals gain some physi- tonian operator H. For molecules with a degenerate Volume 3, September/October 2013 © 2013 John Wiley & Sons, Ltd. 483 Advanced Review wires.wiley.com/wcms or quasi-degenerate GS, linear combinations of a few that substitute the internal orbitals in the CI expan- Slater determinants rather than single Slater determi- sion are called external orbitals, where it is generally nants are eigenfunctions of the spin operators, and assumed that the external orbitals are orthogonal to therefore these spin-adapted configurations are used, the internal orbitals. As internal orbitals, one can use which are called configuration state functions (CSFs). HF canonical orbitals, natural orbitals, Brueckner or- For the purpose of simplifying the notation, we keep bitals, localized orbitals, etc. External orbitals can be the symbol l<t>ff{) to denote a CSF, which in the the virtual orbitals of a HF calculations or any type simplest case is identical to one Slater determinant.
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