Physical Review A

Equation for the direct determination of the density matrix

Hiroshi Nakatsuji

Published Jul 1, 1976• 257 citations

Abstract

A nonvariational equation, called the density equation, is proposed for the direct determination of the density matrix without using a wave function. It is connected with the Schr\"odinger equation by a necessary and sufficient theorem. The equation for the lowest order depends explicitly only on the fourth-order density matrix ${\ensuremath{\Gamma}}^{(4)}$ (or ${\ensuremath{\Gamma}}^{(3)}$ in a special case) and not on the higher-order density matrices. The equation always gives the density matrix and the associated energy which coincide with those obtained indirectly from the Schr\"odinger equation. This is true even if we solve the equation only with the known and tractable $N$-representability conditions, although in such a case some unphysical solution may also occur in the non-$N$-representable space. The equation is applicable to both fermion and boson systems, and to both ground and excited states. In contrast to the Schr\"odinger equation, the labor of solving the equation does not increase when the number of particles of the system is increased. When we have the Hartree-Fock solution, the equation is transformed such that the correlated density matrix and the correlation energy are the direct solution. The correlated density equation thus obtained is suitable for the study of electron correlations.

DOI: 10.1103/physreva.14.41

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Contracted Schrödinger equation: Determining quantum energies and two-particle density matrices without wave functions

David A. Mazziotti

Physical Review AJun 1, 1998389 citations

Direct determination of the quantum-mechanical density matrix: Parquet theory

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Physical Review AJun 1, 199946 citations

Reference-state one-particle density-matrix theory

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Direct Determination of the Quantum-Mechanical Density Matrix Using the Density Equation

Hiroshi Nakatsuji, Koji Yasuda

Physical Review LettersFeb 12, 1996268 citations

Density matrices and density functionals : proceedings of the A. John Coleman symposium

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3,5‐contracted Schrödinger equation: Determining quantum energies and reduced density matrices without wave functions

David A. Mazziotti

International Journal of Quantum ChemistryJan 1, 19985 citations

Physical Review A

Equation for the direct determination of the density matrix

Hiroshi Nakatsuji

Published Jul 1, 1976• 257 citations

Publisher

Abstract

{\ensuremath{\Gamma}}^{(4)}

(or

{\ensuremath{\Gamma}}^{(3)}

in a special case) and not on the higher-order density matrices. The equation always gives the density matrix and the associated energy which coincide with those obtained indirectly from the Schr"odinger equation. This is true even if we solve the equation only with the known and tractable

N

-representability conditions, although in such a case some unphysical solution may also occur in the non-

N

-representable space. The equation is applicable to both fermion and boson systems, and to both ground and excited states. In contrast to the Schr"odinger equation, the labor of solving the equation does not increase when the number of particles of the system is increased. When we have the Hartree-Fock solution, the equation is transformed such that the correlated density matrix and the correlation energy are the direct solution. The correlated density equation thus obtained is suitable for the study of electron correlations.

DOI: 10.1103/physreva.14.41

Related papers

Contracted Schrödinger equation: Determining quantum energies and two-particle density matrices without wave functions

David A. Mazziotti

The contracted Schr\"odinger equation (CSE) technique through its direct determination of the two-particle reduced density matrix (2RDM) without the wave function may offer a fresh alternative to traditional many-body quantum calculations. Without additional information the CSE, also known as the density equation, cannot be solved for the 2RDM because it also requires a knowledge of the 4RDM. We provide theoretical foundations through a reconstruction theorem for recent attempts at generating higher RDMs from the 2RDM to remove the indeterminacy of the CSE. With Grassmann algebra a more concise representation for Valdemoro's reconstruction functionals [F. Colmenero, C. Perez del Valle, and C. Valdemoro, Phys. Rev. A 47, 971 (1993)] is presented. From the perspective of the particle-hole equivalence we obtain Nakatsuji and Yasuda's correction for the 4RDM formula [H. Nakatsuji and K. Yasuda, Phys. Rev. Lett. 76, 1039 (1996)] as well as a corrective approach for the 3RDM functional. A different reconstruction strategy, the ensemble representability method (ERM), is introduced to build the 3- and 4-RDMs by enforcing four-ensemble representability and contraction conditions. We derive the CSE in second quantization without Valdemoro's matrix contraction mapping and offer the first proof of Nakatsuji's theorem for the second-quantized CSE. Both the functional and ERM reconstruction strategies are employed with the CSE to solve for the energies and the 2RDMs of a quasispin model without wave functions. We elucidate the iterative solution of the CSE through an analogy with the power method for eigenvalue equations. Resulting energies of the CSE methods are comparable to single-double configuration-interaction (SDCI) energies, and the 2RDMs are more accurate by an order of magnitude than those from SDCI. While the CSE has been applied to systems with 14 electrons, we present results for as many as 40 particles. Results indicate that the 2RDM remains accurate as the number of particles increases. We also report a direct determination of excited-state 2RDMs through the CSE. By circumventing the wave function, the CSE presents new possibilities for treating electron correlation.The contracted Schr\"odinger equation (CSE) technique through its direct determination of the two-particle reduced density matrix (2RDM) without the wave function may offer a fresh alternative to traditional many-body quantum calculations. Without additional information the CSE, also known as the density equation, cannot be solved for the 2RDM because it also requires a knowledge of the 4RDM. We provide theoretical foundations through a reconstruction theorem for recent attempts at generating higher RDMs from the 2RDM to remove the indeterminacy of the CSE. With Grassmann algebra a more concise representation for Valdemoro's reconstruction functionals [F. Colmenero, C. Perez del Valle, and C. Valdemoro, Phys. Rev. A 47, 971 (1993)] is presented. From the perspective of the particle-hole equivalence we obtain Nakatsuji and Yasuda's correction for the 4RDM formula [H. Nakatsuji and K. Yasuda, Phys. Rev. Lett. 76, 1039 (1996)] as well as a corrective approach for the 3RDM functional. A different reconstruction strategy, the ensemble representability method (ERM), is introduced to build the 3- and 4-RDMs by enforcing four-ensemble representability and contraction conditions. We derive the CSE in second quantization without Valdemoro's matrix contraction mapping and offer the first proof of Nakatsuji's theorem for the second-quantized CSE. Both the functional and ERM reconstruction strategies are employed with the CSE to solve for the energies and the 2RDMs of a quasispin model without wave functions. We elucidate the iterative solution of the CSE through an analogy with the power method for eigenvalue equations. Resulting energies of the CSE methods are comparable to single-double configuration-interaction (SDCI) energies, and the 2RDMs are more accurate by an order of magnitude than those from SDCI. While the CSE has been applied to systems with 14 electrons, we present results for as many as 40 particles. Results indicate that the 2RDM remains accurate as the number of particles increases. We also report a direct determination of excited-state 2RDMs through the CSE. By circumventing the wave function, the CSE presents new possibilities for treating electron correlation.

Physical Review AJun 1, 1998389 citations

Direct determination of the quantum-mechanical density matrix: Parquet theory

Koji Yasuda

The methods used to determine the reduced density matrix (RDM) of the ground and excited states, the finite-temperature systems, and the large systems without using the wave function by solving the density equation were discussed. We examined the foundations to reconstruct the higher-order RDMs of the ground and excited states and the finite-temperature systems in terms of the lower-order RDMs. We presented the equation to determine the RDMs of the finite-temperature systems directly and showed that only the exact RDMs satisfy the equation. Our previous approximation for third- and fourth-order RDMs of the ground state [H. Nakatsuji and K. Yasuda, Phys. Rev. Lett. 76, 1039 (1996)] was reformulated, and the accuracy of this approximation for the excited states was examined. The structure of the $n\mathrm{th}$ order energy density matrix $(n$ -EDM) was analyzed, and the calculation method which sums up the Parquet diagram of the 2-EDM without explicitly constructing the third- and fourth-order RDMs was reported. This approximation is more accurate than the previous second-order approximation and also includes the infinite series of bubble and ladder Green's function diagrams. Such a method is necessary to apply the density-equation method to large systems, such as polymers, metals, and semiconductors. The new approximation together with the density equation was applied to the ground states of some molecules including CO, ${\mathrm{C}}_{2}{\mathrm{H}}_{2},$ ${\mathrm{C}}_{3}{\mathrm{H}}_{8}$ , and ${\mathrm{C}}_{4}{\mathrm{H}}_{10},$ and the excited states of the Be atom and ${\mathrm{Li}}_{2}$ molecule. The calculated energies were as accurate as the exact or coupled-cluster single and double excitations with triples included noniteratively, and the energy errors of the second-order approximation were significantly reduced. The calculated 2-RDMs almost satisfied important representability conditions while the 1-RDMs were exactly ensemble representable. These results demonstrate that the density equation offers a new quantitative method for treating electron correlations. The relationship between the iterative procedure and the finite-temperature density-equation method was discussed.The methods used to determine the reduced density matrix (RDM) of the ground and excited states, the finite-temperature systems, and the large systems without using the wave function by solving the density equation were discussed. We examined the foundations to reconstruct the higher-order RDMs of the ground and excited states and the finite-temperature systems in terms of the lower-order RDMs. We presented the equation to determine the RDMs of the finite-temperature systems directly and showed that only the exact RDMs satisfy the equation. Our previous approximation for third- and fourth-order RDMs of the ground state [H. Nakatsuji and K. Yasuda, Phys. Rev. Lett. 76, 1039 (1996)] was reformulated, and the accuracy of this approximation for the excited states was examined. The structure of the $n\mathrm{th}$ order energy density matrix $(n$-EDM) was analyzed, and the calculation method which sums up the Parquet diagram of the 2-EDM without explicitly constructing the third- and fourth-order RDMs was reported. This approximation is more accurate than the previous second-order approximation and also includes the infinite series of bubble and ladder Green's function diagrams. Such a method is necessary to apply the density-equation method to large systems, such as polymers, metals, and semiconductors. The new approximation together with the density equation was applied to the ground states of some molecules including CO, ${\mathrm{C}}_{2}{\mathrm{H}}_{2},$ ${\mathrm{C}}_{3}{\mathrm{H}}_{8}$, and ${\mathrm{C}}_{4}{\mathrm{H}}_{10},$ and the excited states of the Be atom and ${\mathrm{Li}}_{2}$ molecule. The calculated energies were as accurate as the exact or coupled-cluster single and double excitations with triples included noniteratively, and the energy errors of the second-order approximation were significantly reduced. The calculated 2-RDMs almost satisfied important representability conditions while the 1-RDMs were exactly ensemble representable. These results demonstrate that the density equation offers a new quantitative method for treating electron correlations. The relationship between the iterative procedure and the finite-temperature density-equation method was discussed.

Physical Review AJun 1, 199946 citations

Reference-state one-particle density-matrix theory

James P. Finley

A density-matrix formalism is developed based on the one-particle density-matrix of a single-determinantal reference state. Unlike traditional density-functional-theory approaches, the $v$ -representable problem does not appear in the proposed method, nor the need to introduce functionals defined by a constrained search. The correlation-energy functionals are nonuniversal, in the sense that they depend on the external potential. Nevertheless, model systems can still be used to derive universal energy functionals. Variational and nonvariational energy functionals are introduced that yield the target-state energy when the reference state---or its corresponding one-particle density matrix---is constructed from Brueckner orbitals. Nonvariational energy functionals yield generalized Hartree-Fock equations involving a nonlocal correlation potential and the Hartree-Fock exchange operator; these equations are obtained by imposing the Brillouin-Brueckner condition. The same equations---for the most part---are obtained from variational energy functionals using functional minimization, yielding the (kernel of the) correlation potential as the functional derivative of correlation-energy functionals. Approximations for the correlation-energy functions are introduced, including a one-particle-density-matrix variant of the local-density approximation, a variant of the Colle-Salvetti functional, and a linear combination of the two that is a variant of the correlation-energy functional within the hybrid, three-parameter, Becke-Lee-Yang-Parr density functional (B3LYP).A density-matrix formalism is developed based on the one-particle density-matrix of a single-determinantal reference state. Unlike traditional density-functional-theory approaches, the $v$-representable problem does not appear in the proposed method, nor the need to introduce functionals defined by a constrained search. The correlation-energy functionals are nonuniversal, in the sense that they depend on the external potential. Nevertheless, model systems can still be used to derive universal energy functionals. Variational and nonvariational energy functionals are introduced that yield the target-state energy when the reference state---or its corresponding one-particle density matrix---is constructed from Brueckner orbitals. Nonvariational energy functionals yield generalized Hartree-Fock equations involving a nonlocal correlation potential and the Hartree-Fock exchange operator; these equations are obtained by imposing the Brillouin-Brueckner condition. The same equations---for the most part---are obtained from variational energy functionals using functional minimization, yielding the (kernel of the) correlation potential as the functional derivative of correlation-energy functionals. Approximations for the correlation-energy functions are introduced, including a one-particle-density-matrix variant of the local-density approximation, a variant of the Colle-Salvetti functional, and a linear combination of the two that is a variant of the correlation-energy functional within the hybrid, three-parameter, Becke-Lee-Yang-Parr density functional (B3LYP).

arXiv:physics/0308056Physical Review AApr 1, 20044 citations

Direct Determination of the Quantum-Mechanical Density Matrix Using the Density Equation

Hiroshi Nakatsuji, Koji Yasuda

With the use of the density equation [H. Nakatsuji, Phys. Rev. A 14, 41 (1976)], the second-order density matrices are directly determined without any use of the wave functions. The third- and fourth-order reduced density matrices (RDM's) are decoupled into lower-order ones using the Green's function technique. This method is applied to Be, Ne, ${\mathrm{H}}_{2}$ O, ${H}_{3}{O}^{+}$ , N ${\mathrm{H}}_{3}$ , C ${\mathrm{H}}_{4}$ , ${\mathrm{BH}}_{4}^{\phantom{\rule{0ex}{0ex}}\ensuremath{-}}$, ${\mathrm{NH}}_{4}^{\phantom{\rule{0ex}{0ex}}+}$ , and C ${\mathrm{H}}_{3}$ F, and the results are successfully compared with the full configuration interaction results. The convergence is fairly good, and the calculated second-order RDM's almost satisfy the necessary conditions of the N representability, the P, Q, and G conditions, and the first-order RDM's are exactly N representable. These results show that the present method is very promising.With the use of the density equation [H. Nakatsuji, Phys. Rev. A 14, 41 (1976)], the second-order density matrices are directly determined without any use of the wave functions. The third- and fourth-order reduced density matrices (RDM's) are decoupled into lower-order ones using the Green's function technique. This method is applied to Be, Ne, ${\mathrm{H}}_{2}$O, ${H}_{3}{O}^{+}$, N${\mathrm{H}}_{3}$, C${\mathrm{H}}_{4}$, ${\mathrm{BH}}_{4}^{\phantom{\rule{0ex}{0ex}}\ensuremath{-}}$, ${\mathrm{NH}}_{4}^{\phantom{\rule{0ex}{0ex}}+}$, and C${\mathrm{H}}_{3}$F, and the results are successfully compared with the full configuration interaction results. The convergence is fairly good, and the calculated second-order RDM's almost satisfy the necessary conditions of the N representability, the P, Q, and G conditions, and the first-order RDM's are exactly N representable. These results show that the present method is very promising.

Physical Review LettersFeb 12, 1996268 citations

Density matrices and density functionals : proceedings of the A. John Coleman symposium

Alan Coleman, Robert Erdahl, Vedene H. Smith

A Tribute to A. John Coleman - The Tame Mathematician.- Reduced Density Matrices: 1929-1989.- Some Aspects on the Development of the Theory of Reduced Density Matrices and the Representability Problem.- Representability Conditions.- On the Diagonal N-Representability Problem.- Fermion N-Representability Conditions Generated by a Decomposition of the 1-Particle Identity Operator onto Mutually Orthogonal Projection Operators.- The Unitarily Invariant Decomposition of Hermitian Operators.- Building Up N-Electron States with Symplectic Symmetry.- Time Dependent Antisymmetrized Geminal Power Theory Using a Coherent State Formulation.- Griffiths Inequalities for Fermion Systems.- Entropy of Reduced Density Matrices.- A Lower Bound to the Ground State Energy of a Boson System With Fermion Source.- Reduced Density Operators, Their Related von Neumann Density Operators, Close Cousins of These, and Their Physical Interpretation.- Theory and Practice of the Spin-Adapted Reduced Hamiltonians (SRH).- Variational Principle with Built-In Pure State N-Representability Conditions. The N-Electron Case.- Wigner Distributions as Representations of the Density Matrix.- Inter-Relationships Between Various Representations of One-Matrices and Related Densities: A Road Map and an Example ..- Current Problems in Density Functional Theory.- The Interface Between Reduced Density Matrices and Density Functional Theory.- The Physics Underlying the Langreth-Mehl Scheme for Non-Uniform Systems.- Understanding Energy Differences in Density Functional Theory.- Density Functional Calculations of Molecular Bond Energies.- Non-Local Effects on Atomic and Molecular Correlation Energies Studied with a Gradient-Corrected Density Functional.- An Evaluation of Local Electron Correlation Corrections and Non-Local Exchange Corrections to the Hartree-Fock-Slater Method from Calculations on Bond Energies and Electronic Spectra of Molecular Systems.- Correlation Energy Functionals of One-Matrices and Hartree-Fock Densities.- Some Remarks on Scaling Relations in Density Functional Theory.- Deduction of Semiempirical MO Methods from Density Functional Theory.- Charge and Spin Densities in Molecular Solids: Local Density Functional Calculations Versus Experiment.- A Functional of the Two-Particle Density Matrix for the Approximate Calculation of the Electronic Correlation Energy.- Extracules, Intracules, Correlation Holes, Potentials, Coefficients and All That.- The Exact Schroedinger Equation for the Electron Density.- Adiabatic Separation, Broken Symmetries and Geometry Optimization.- Asymptotic Results for Density Matrices and Electron Density in Atoms and Nearly Spherical Molecules.- An Algorithm for Calculating Isoelectronic Changes in Energies, Densities, and One-Matrices.- Atoms and Ions in the Limit of Large Nuclear Charge.- Improved Thomas-Fermi Theory for Atoms.- A Bond Energy from Quantum Mechanics.- Measured Electron Densities and Band Structure Calculations.- X-ray Orthonormal Orbital Model for Crystallography.A Tribute to A. John Coleman - The Tame Mathematician.- Reduced Density Matrices: 1929-1989.- Some Aspects on the Development of the Theory of Reduced Density Matrices and the Representability Problem.- Representability Conditions.- On the Diagonal N-Representability Problem.- Fermion N-Representability Conditions Generated by a Decomposition of the 1-Particle Identity Operator onto Mutually Orthogonal Projection Operators.- The Unitarily Invariant Decomposition of Hermitian Operators.- Building Up N-Electron States with Symplectic Symmetry.- Time Dependent Antisymmetrized Geminal Power Theory Using a Coherent State Formulation.- Griffiths Inequalities for Fermion Systems.- Entropy of Reduced Density Matrices.- A Lower Bound to the Ground State Energy of a Boson System With Fermion Source.- Reduced Density Operators, Their Related von Neumann Density Operators, Close Cousins of These, and Their Physical Interpretation.- Theory and Practice of the Spin-Adapted Reduced Hamiltonians (SRH).- Variational Principle with Built-In Pure State N-Representability Conditions. The N-Electron Case.- Wigner Distributions as Representations of the Density Matrix.- Inter-Relationships Between Various Representations of One-Matrices and Related Densities: A Road Map and an Example ..- Current Problems in Density Functional Theory.- The Interface Between Reduced Density Matrices and Density Functional Theory.- The Physics Underlying the Langreth-Mehl Scheme for Non-Uniform Systems.- Understanding Energy Differences in Density Functional Theory.- Density Functional Calculations of Molecular Bond Energies.- Non-Local Effects on Atomic and Molecular Correlation Energies Studied with a Gradient-Corrected Density Functional.- An Evaluation of Local Electron Correlation Corrections and Non-Local Exchange Corrections to the Hartree-Fock-Slater Method from Calculations on Bond Energies and Electronic Spectra of Molecular Systems.- Correlation Energy Functionals of One-Matrices and Hartree-Fock Densities.- Some Remarks on Scaling Relations in Density Functional Theory.- Deduction of Semiempirical MO Methods from Density Functional Theory.- Charge and Spin Densities in Molecular Solids: Local Density Functional Calculations Versus Experiment.- A Functional of the Two-Particle Density Matrix for the Approximate Calculation of the Electronic Correlation Energy.- Extracules, Intracules, Correlation Holes, Potentials, Coefficients and All That.- The Exact Schroedinger Equation for the Electron Density.- Adiabatic Separation, Broken Symmetries and Geometry Optimization.- Asymptotic Results for Density Matrices and Electron Density in Atoms and Nearly Spherical Molecules.- An Algorithm for Calculating Isoelectronic Changes in Energies, Densities, and One-Matrices.- Atoms and Ions in the Limit of Large Nuclear Charge.- Improved Thomas-Fermi Theory for Atoms.- A Bond Energy from Quantum Mechanics.- Measured Electron Densities and Band Structure Calculations.- X-ray Orthonormal Orbital Model for Crystallography.

D. Reidel Pub. Co. eBooksJan 1, 198719 citations

3,5‐contracted Schrödinger equation: Determining quantum energies and reduced density matrices without wave functions

David A. Mazziotti

Through the 3,5-contracted Schrödinger equation (3,5-CSchE) quantum energies and 3-particle reduced density matrices (3-RDMs) are determined directly without wave functions. Since the 3,5-CSchE involves the 5-RDM, its solution is indeterminate without N-representability conditions. However, the indeterminacy of the 3,5-CSchE may be removed through a reconstruction strategy for building the 4- and 5-RDMs from the 3-RDM. We present a systematic procedure for obtaining corrections for Valdemoro's reconstruction functionals from two complementary approaches, the particle–hole duality and the theory of cumulants. With the cumulants we are able to demonstrate that we have obtained all terms in the reconstruction functionals which may be written as antisymmetric products of the lower rdms. The cumulants allow us to understand the reconstruction functionals in terms of a renormalized many-body perturbation theory. The reconstruction functionals also lead to a natural generalization of Wick's theorem for evaluating expectation values of fermionic annihilation and creation operators with respect to correlated reference states. Previous work [Phys. Rev. A 57, 4219 (1998)] has explored the determination of correlation energy and 2-RDMs through the 2,4-CSchE, also known as the density equation. Because the reconstruction functionals employed with the 3,5-CSchE depend only on the antisymmetric products of lower RDMs in constrast to those used with the 2,4-CSchE, the 3,5-CSchE method presented here does not require the solution of systems of linear equations during reconstruction or the storage of the reconstructed RDMs. Application of the 3,5-CSchE technique to a quasi-spin model generates ground-state energies and 2-RDMs similar in accuracy to single–double configuration interaction (SDCI). We employ a simple iterative procedure for the solution of the 3,5-CSchE without traditional diagonalization. The CSchE techniques offer an approximate solution of the N-representability problem and a new approach to electron correlation. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 557–570, 1998Through the 3,5-contracted Schrödinger equation (3,5-CSchE) quantum energies and 3-particle reduced density matrices (3-RDMs) are determined directly without wave functions. Since the 3,5-CSchE involves the 5-RDM, its solution is indeterminate without N-representability conditions. However, the indeterminacy of the 3,5-CSchE may be removed through a reconstruction strategy for building the 4- and 5-RDMs from the 3-RDM. We present a systematic procedure for obtaining corrections for Valdemoro's reconstruction functionals from two complementary approaches, the particle–hole duality and the theory of cumulants. With the cumulants we are able to demonstrate that we have obtained all terms in the reconstruction functionals which may be written as antisymmetric products of the lower rdms. The cumulants allow us to understand the reconstruction functionals in terms of a renormalized many-body perturbation theory. The reconstruction functionals also lead to a natural generalization of Wick's theorem for evaluating expectation values of fermionic annihilation and creation operators with respect to correlated reference states. Previous work [Phys. Rev. A 57, 4219 (1998)] has explored the determination of correlation energy and 2-RDMs through the 2,4-CSchE, also known as the density equation. Because the reconstruction functionals employed with the 3,5-CSchE depend only on the antisymmetric products of lower RDMs in constrast to those used with the 2,4-CSchE, the 3,5-CSchE method presented here does not require the solution of systems of linear equations during reconstruction or the storage of the reconstructed RDMs. Application of the 3,5-CSchE technique to a quasi-spin model generates ground-state energies and 2-RDMs similar in accuracy to single–double configuration interaction (SDCI). We employ a simple iterative procedure for the solution of the 3,5-CSchE without traditional diagonalization. The CSchE techniques offer an approximate solution of the N-representability problem and a new approach to electron correlation. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 557–570, 1998

International Journal of Quantum ChemistryJan 1, 19985 citations

{\ensuremath{\Gamma}}^{(4)}

(or

{\ensuremath{\Gamma}}^{(3)}

N

-representability conditions, although in such a case some unphysical solution may also occur in the non-

N

n\mathrm{th}

order energy density matrix

(n

-EDM) was analyzed, and the calculation method which sums up the Parquet diagram of the 2-EDM without explicitly constructing the third- and fourth-order RDMs was reported. This approximation is more accurate than the previous second-order approximation and also includes the infinite series of bubble and ladder Green's function diagrams. Such a method is necessary to apply the density-equation method to large systems, such as polymers, metals, and semiconductors. The new approximation together with the density equation was applied to the ground states of some molecules including CO,

{\mathrm{C}}_{2}{\mathrm{H}}_{2},

{\mathrm{C}}_{3}{\mathrm{H}}_{8}

, and

{\mathrm{C}}_{4}{\mathrm{H}}_{10},

and the excited states of the Be atom and

{\mathrm{Li}}_{2}

molecule. The calculated energies were as accurate as the exact or coupled-cluster single and double excitations with triples included noniteratively, and the energy errors of the second-order approximation were significantly reduced. The calculated 2-RDMs almost satisfied important representability conditions while the 1-RDMs were exactly ensemble representable. These results demonstrate that the density equation offers a new quantitative method for treating electron correlations. The relationship between the iterative procedure and the finite-temperature density-equation method was discussed.

A density-matrix formalism is developed based on the one-particle density-matrix of a single-determinantal reference state. Unlike traditional density-functional-theory approaches, the

v

-representable problem does not appear in the proposed method, nor the need to introduce functionals defined by a constrained search. The correlation-energy functionals are nonuniversal, in the sense that they depend on the external potential. Nevertheless, model systems can still be used to derive universal energy functionals. Variational and nonvariational energy functionals are introduced that yield the target-state energy when the reference state---or its corresponding one-particle density matrix---is constructed from Brueckner orbitals. Nonvariational energy functionals yield generalized Hartree-Fock equations involving a nonlocal correlation potential and the Hartree-Fock exchange operator; these equations are obtained by imposing the Brillouin-Brueckner condition. The same equations---for the most part---are obtained from variational energy functionals using functional minimization, yielding the (kernel of the) correlation potential as the functional derivative of correlation-energy functionals. Approximations for the correlation-energy functions are introduced, including a one-particle-density-matrix variant of the local-density approximation, a variant of the Colle-Salvetti functional, and a linear combination of the two that is a variant of the correlation-energy functional within the hybrid, three-parameter, Becke-Lee-Yang-Parr density functional (B3LYP).

{\mathrm{H}}_{2}

{H}_{3}{O}^{+}

, N

{\mathrm{H}}_{3}

, C

{\mathrm{H}}_{4}

, ${\mathrm{BH}}_{4}^{\phantom{\rule{0ex}{0ex}}\ensuremath{-}}$,

{\mathrm{NH}}_{4}^{\phantom{\rule{0ex}{0ex}}+}

, and C

{\mathrm{H}}_{3}

F, and the results are successfully compared with the full configuration interaction results. The convergence is fairly good, and the calculated second-order RDM's almost satisfy the necessary conditions of the N representability, the P, Q, and G conditions, and the first-order RDM's are exactly N representable. These results show that the present method is very promising.