The Coupled Cluster (CC) method is a widely used and highly successful high precision method for the solution of the stationary electronic Schrödinger equation, with its practical convergence properties being similar to that of a corresponding Galerkin (CI) scheme. This behaviour has for the discrete CC method been analyzed with respect to the discrete Galerkin solution (the “full-CI-limit”) in [Schneider, 2009]. Recently, we globalized the CC formulation to the full continuous space, giving a root equation for an infinite dimensional, nonlinear Coupled Cluster operator that is equivalent the full electronic Schrödinger equation [Rohwedder, 2011]. In this paper, we combine both approaches to prove existence and uniqueness results, quasi-optimality estimates and energy estimates for the CC method with respect to the solution of the full, original Schrödinger equation. The main property used is a local strong monotonicity result for the Coupled Cluster function, and we give two characterizations for situations in which this property holds.
Mots-clés : quantum chemistry, electronic Schrödinger equation, coupled cluster method, numerical analysis, nonlinear operator equation, quasi-optimality, error estimators
@article{M2AN_2013__47_6_1553_0,
author = {Rohwedder, Thorsten and Schneider, Reinhold},
title = {Error estimates for the {Coupled} {Cluster} method},
journal = {ESAIM: Mathematical Modelling and Numerical Analysis },
pages = {1553--1582},
publisher = {EDP-Sciences},
volume = {47},
number = {6},
year = {2013},
doi = {10.1051/m2an/2013075},
mrnumber = {3110488},
zbl = {1297.65139},
language = {en},
url = {http://archive.numdam.org/articles/10.1051/m2an/2013075/}
}
TY - JOUR AU - Rohwedder, Thorsten AU - Schneider, Reinhold TI - Error estimates for the Coupled Cluster method JO - ESAIM: Mathematical Modelling and Numerical Analysis PY - 2013 SP - 1553 EP - 1582 VL - 47 IS - 6 PB - EDP-Sciences UR - http://archive.numdam.org/articles/10.1051/m2an/2013075/ DO - 10.1051/m2an/2013075 LA - en ID - M2AN_2013__47_6_1553_0 ER -
%0 Journal Article %A Rohwedder, Thorsten %A Schneider, Reinhold %T Error estimates for the Coupled Cluster method %J ESAIM: Mathematical Modelling and Numerical Analysis %D 2013 %P 1553-1582 %V 47 %N 6 %I EDP-Sciences %U http://archive.numdam.org/articles/10.1051/m2an/2013075/ %R 10.1051/m2an/2013075 %G en %F M2AN_2013__47_6_1553_0
Rohwedder, Thorsten; Schneider, Reinhold. Error estimates for the Coupled Cluster method. ESAIM: Mathematical Modelling and Numerical Analysis , Tome 47 (2013) no. 6, pp. 1553-1582. doi : 10.1051/m2an/2013075. http://archive.numdam.org/articles/10.1051/m2an/2013075/
[1] and , Existence of minimizers for Kohn − Sham models in quantum chemistry. Ann. Institut Henri Poincaré, Non Linear Anal. 26 (2009) 2425. | Numdam | MR | Zbl
[2] , Lectures on exponential decay of solutions of second-order elliptic equations. Princeton University press, Princeton (1982). | MR | Zbl
[3] , Lineare Funktionalanalysis, Auflage. Springer, Berlin 5 (2006). | Zbl
[4] , Variational principles and linked-cluster exp S expansions for static and dynamic many-body problems. Ann. Phys. 151 (1983) 311.
[5] and , Automatic Code Generation for Many-Body Electronic Structure Methods: The tensor contraction engine. Molecul. Phys. 104 (2006) 211.
[6] and , Finite Element-Galerkin Approximation of the Eigenvalues and Eigenvectors of Selfadjoint Problems. Math. Comput. 52 (1989) 275-297. | MR | Zbl
[7] , , and , There are no unfilled shells in unrestricted Hartree-Fock theory. Phys. Rev. Lett. 72 (1994) 2981.
[8] and , Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms: Coupled cluster and multireference methods. J. Chem. Phys. 125 (2006) 074110.
[9] and , Adaptive finite element methods for differential equations. Birkhäuser (2003). | MR | Zbl
[10] , Many-body perturbation theory and coupled cluster theory for electronic correlation in molecules. Ann. Rev. Phys. Chem. 32 (1981) 359.
[11] and , Coupled-cluster theory in quantum chemistry. Rev. Mod. Phys. 79 (2007) 291.
[12] and , Many-body perturbation theory, coupled-pair many-electron theory, and the importance of quadruple excitations for the correlation problem. Int. J. Quantum Chem. 14 (1978) 561.
[13] and , An optimal control approach to error estimation and mesh adaptation in finite element methods. Acta Numerica 2000. Edited by A. Iserles. Cambridge University Press (2001) 1. | MR | Zbl
[14] , , and , A new Approach for Tensor Decomposition in Electronic Structure Theory (submitted).
[15] and , A Critical Assessment of Multireference-Fock Space CCSD and Perturbative Third-Order Triples Approximations for Photoelectron Spectra and Quasidegenerate Potential Energy Surfaces. Adv. Quantum Chemist. 34 (1999) 261.
[16] , An overview of coupled cluster theory and its applications in physics. Theor. Chim. Acta 80 (1991) 95.
[17] and , Zur Quantentheorie der Molekeln. Ann. Phys. 389 (1927) 457. | JFM
[18] , and , Numerical Analysis of Nonlinear Eigenvalue Problems J. Scientific Comput. 45 (2010) 90. DOI: 10.1007/s10915-010-9358-1. | MR | Zbl
[19] , and , Recent Progress in Coupled Cluster Methods, Theory and Applications. In vol. 44 of series: Challenges Adv. Comput. Chem. Phys. Springer (2010).
[20] , , , , , , , , , , , , , and , Encyclopedia Appl. Comput. Math. Springer. To appear (2013).
[21] , Coupled cluster theory with emphasis on selected new developments. Theor. Chem. Acc. 116 (2006) 106.
[22] and , Handbook of Numerical Analysis, Volume II: Finite Element Methods (Part I). Elsevier (1991). | MR | Zbl
[23] and , Handbook of Numerical Analysis, Volume X: Special Volume. Computational Chemistry. Elsevier (2003). | Zbl
[24] , Origins of coupled cluster technique for atoms and molecules. Theor. Chim. Acta 80 (1991) 91.
[25] , Bound states of a many-particle system. Nucl. Phys. 7 (1958) 421.
[26] and , Short range correlations in nuclear wave functions. Nucl. Phys. 17 (1960) 477. | MR | Zbl
[27] Computational Chemistry Comparison and Benchmark Data Base, National Institute of Standards and Technology. Available on www.cccbdb.nist.gov.
[28] and , An introduction to coupled cluster theory for computational chemists. Rev. Comput. Chem. 14 (2000) 33.
[29] Dalgaard and H.J. Monkhorst, Some aspects of the time-dependent coupled-cluster approach to dynamic response functions. Phys. Rev. A 28 (1983) 1217.
[30] and , Numerical Methods for Unconstrained Optimization and Nonlinear Equations. SIAM, Philadelphia (1996). | MR | Zbl
[31] , Quantum Mechanics of Many-Electron Systems. Proc. of Royal Soc. London, Series A CXXIII (1929) 714. | JFM
[32] and , Density functional theory. Springer (1990). | Zbl
[33] , Gewöhnliche und Operator-Differentialgleichungen, Vieweg (2004).
[34] , and , Adaptive methods in Quantum Chemistry. Zeitsch. f. Phys. Chem. 224 (2010) 651-670.
[35] , Konfigurationsraum und zweite Quantelung. Z. Phys. 75 (1932) 622. | Zbl
[36] and , Explicit large nuclear charge limit of electronic ground states for Li, Be, B, C, N, O, F, Ne and basic aspects of the periodic table. SIAM J. Math. Anal. 41 (2009) 631-664. | MR | Zbl
[37] , and , Nichtlineare Operatorgleichungen und Operatordifferentialgleichungen, Akademie Verlag (1974). | MR | Zbl
[38] and , A second-order correction to singles and doubles coupled-cluster methods based on a perturbative expansion of a similarity-transformed Hamiltonian 323 (2000) 2128.
[39] , , and , Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model. J. Chem. Phys. 113 (2000) 3548-3560.
[40] , Elliptic Differential Equations, vol. 18. of SSCM. Springer (1992), | MR | Zbl
[41] and , Local treatment of electron correlation in coupled cluster theory. J. Chem. Phys. 104 (1996) 6286.
[42] and , Configuration-interaction energy derivatives in a fully variational formulation. Theor. Chim. Acta 75 (1989) 111127.
[43] , and , Molecular Electronic-Structure Theory. John Wiley & Sons (2000).
[44] , and , Quantitative quantum chemistry. Mol. Phys. 106 (2008) 2107.
[45] , Tensor contraction engine: Abstraction and automated parallel implementation of Configuration-Interaction, Coupled-Cluster, and Many-Body perturbation theories. J. Phys. Chem. A 46 (2003) 9887.
[46] and , The quantum N-body problem. J. Math. Phys. 41 (2000) 6. | MR | Zbl
[47] W. Klopper, F.R. Manby, S. Ten-no and E.F. Vallev, R12 methods in explicitly correlated molecular structure theory. Int. Rev. Phys. Chem. 25 (2006) 427.
[48] , and , Ab Initio Methods for Electron Correlation in Molecules, Modern Methods and Algorithms of Quantum Chemistry, vol. 3 of Proceedings, Second Edition, edited by J. Grotendorst. John von Neumann Institute for Computing, Jülich, NIC Series, ISBN 3-00-005834-6 (2000) 97-179.
[49] and , Fifth-order many-body perturbation theory and its relationship to various coupled-cluster approaches. Adv. Quantum Chem. 18 (1986) 281.
[50] , Error analysis and improvement of coupled cluster theory, Theoretica Chimica Acta 80 (1991) 349.
[51] , Compound pair states in imperfect Fermi gases. Nucl. Phys. 22 (1961) 177. | MR | Zbl
[52] , and , Many-fermion theory in expS- (or coupled cluster) form. Phys. Reports 36 (1978) 1.
[53] , Ab initio quantum dynamics using coupled-cluster, to appear in J. Chem. Phys. (2012).
[54] , Comparison of the T1 and D1 diagnostics for electronic structure theory: a new definition for the open-shell D1 diagnostic. Chem. Phys. Lett. 372 (2003) 362-367.
[55] and , Achieving chemical accuracy with Coupled Cluster methods, in Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy, edited by S.R. Langhof. Kluwer Academic Publishers, Dordrecht (1995) 47.
[56] and , A diagnostic for determining the quality of single-reference electron correlation methods. Int. J. Quantum Chem. Symp. 23 (1989) 199-207.
[57] and , Dissociation of N2 triple bond: a reduced multireference CCSD study. Chem. Phys. Lett. 286 12 (1998) 145-154.
[58] and , The Hartree − Fock Theory for Coulomb Systems. Commun. Math. Phys. 53 (1977) 185. | MR
[59] , Bound on the maximum negative ionization of atoms and molecules. Phys. Rev. A 29 (1984) 3018.
[60] and , Atomic Many-body Theory. Springer (1986).
[61] , Solution of the Hartree Fock equation for Coulomb Systems. Commun. Math. Phys. 109 (1987) 33. | MR | Zbl
[62] , From Quantum to Classical Molecular Dynamics: Reduced methods and Numerical Analysis. Zürich Lect. Adv. Math. EMS (2008). | MR | Zbl
[63] , and , State-specific multireference complete-active-space coupled-cluster approach versus other quantum chemical methods: dissociation of the N2 molecule. Mol. Phys. 105 (2007) 1335-1357.
[64] and , An adaptive coupled-cluster theory: @CC approach. J. Chem. Phys. 133 (2010) 244112.
[65] , and , Efficient and accurate approximations to the local coupled cluster singles doubles method using a truncated pair natural orbital basis. J. Chem. Phys. 131 (2009) 064103.
[66] , and , A size-consistent state-specific multireference coupled cluster theory: Formal developments and molecular applications. J. Chem. Phys. 110 (1999) 6171-6188.
[67] , and , Reflections on size-extensivity, size-consistency and generalized extensivity in many-body theory. Molecular Phys. 103 (2005) 2277.
[68] , Coupled Cluster Theory, in Methods Comput. Molec. Phys., edited by S. Wilson and G.F.H. Diercksen. Plenum. New York (1992) 99.
[69] , and , Degeneracy and coupled-cluster Approaches 26 (1984) 237-244.
[70] and , Density-Functional Theory of Atoms and Molecules. Oxford University Press (1994).
[71] , Bounds for the discrete part of the spectrum of a semibounded Schrödinger operator. Math. Scand. 8 (1960) 143. | MR | Zbl
[72] , and , A state-selective multireference coupled-cluster theory employing the single-reference formalism. J. Chem. Phys. 99 (1993) 1875.
[73] , , and , New alternatives for electronic structure calculations: Renormalized, extended, and generalized coupled-cluster theories, in vol. 12 of Progr. Theoret. Chemist. Phys., edited by J. Maruani, R. Lefebvre, E. Brändas. Kluwer, Dordrecht (2003) 119-206.
[74] and , Consistenct, stability, a priori and a posteriori estimates for Petrov-Galerkin methods applied to nonlinear problems. Num. Math. 69 (1994) 213-231. | MR | Zbl
[75] , , and , A fifth-order perturbation comparison of electronic correlation theories. Chem. Phys. Lett. 157 (1989) 479.
[76] , A Theoretical Challenge: Transition-Metal Compounds, Chimia 63 (2009) 140-145.
[77] and , Methods of Modern Mathematical Physics IV - Analysis of operators. Academic Press (1978). | MR | Zbl
[78] , An analysis for some methods and algorithms of Quantum Chemistry, Ph.D. thesis, TU Berlin, available at http://opus.kobv.de/tuberlin/volltexte/2010/2852/ (2010).
[79] , The continuous Coupled Cluster formulation for the electronic Schrödinger equation, submitted to M2AN. | Numdam | Zbl
[80] , Functional Analysis. Tat McGraw & Hill Publishing Company, New Delhi (1979). | MR | Zbl
[81] , and , Numerical Methods for Electronic Structure Calculations of Materials. SIAM Rev. 52 (2010) 1. | MR | Zbl
[82] , Analysis of the projected Coupled Cluster method in electronic structure calculation. Num. Math. 113 (2009) 433. | MR | Zbl
[83] and , Low-order scaling local correlation methods. IV. Linear scaling coupled cluster (LCCSD). J. Chem. Phys. 114 (2000) 661.
[84] , Schrödinger operators in the 20th century. J. Math. Phys. 41 (2000) 3523. | MR | Zbl
[85] and , Modern Quantum Chemistry. Dover Publications Inc. (1992).
[86] , Stability conditions and nuclear rotations in the Hartree − Fock theory. Nuclear Phys. 21 (1960) 225. | MR | Zbl
[87] , Partial differential equations. Cambridge University Press, reprint (1992). | MR | Zbl
[88] , Regularity and Approximability of Electronic Wave Functions, in vol. 2000 of Lect. Notes Math. Ser. Springer-Verlag (2010). | MR | Zbl
[89] , Nonlinear Functional Analysis and Its Applications, Part II B: Nonlinear Monotone Operators. Springer (1990). | MR | Zbl
[90] , Discussion of the spectrum of Schrödinger operator for systems of many particles. Trudy Mosov. Mat. Obshch. 9 (1960) 81-128. | Zbl
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