Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

The Journal of Chemical Physics

Normal order and extended Wick theorem for a multiconfiguration reference wave function

Werner Kutzelnigg, Debashis Mukherjee

Published Jul 8, 1997• 301 citations
Publisher

Abstract

A generalization of normal ordering and of Wick’s theorem with respect to an arbitrary reference function Φ as some generalized “physical vacuum” is formulated in a different (but essentially equivalent) way than that suggested previously by one of the present authors. Guiding principles are that normal order operators with respect to any reference state must be expressible as linear combinations of those with respect to the genuine vacuum, that the vacuum expectation value of a normal order operator must vanish (with respect to the vacuum to which it is in normal order), and that the well-known formalism for a single Slater determinant as physical vacuum must be contained as a special case. The derivation is largely based on the concepts of “Quantum Chemistry in Fock space,” which means that particle-number-conserving operators (excitation operators) play a central role. Nevertheless, the contraction rules in the frame of a generalized Wick theorem are derived, that hold for non-particle-number-conserving operators as well. The contraction rules are formulated and illustrated in terms of diagrams. The contractions involve the “residual n-particle density matrices” λ, which are the irreducible (non-factorizable) parts of the conventional n-particle density matrices γ, in the sense of a cumulant expansion for the density. A spinfree formulation is presented as well. The expression of the Hamiltonian in normal order with respect to a multiconfiguration reference function leads to a natural definition of a generalized Fock operator. MC-SCF-theory is easily worked out in this context. The paper concludes with a discussion of the excited configurations and the first-order interacting space, that underlies a perturbative coupled cluster type correction to the MCSCF function for an arbitrary reference function, and with general implications of the new formalism, that is related to “internally contracted multireference configuration interaction.” The present generalization of normal ordering is not only valid for arbitrary reference functions, but also if the reference state is an ensemble state.

DOI
10.1063/1.474405

Related papers

Irreducible Brillouin conditions and contracted Schrödinger equations for n -electron systems. I. The equations satisfied by the density cumulants

Debashis Mukherjee, Werner Kutzelnigg

Two alternative conditions for the stationarity of the energy expectation value with respect to k-particle excitations are the k-particle Brillouin conditions BCk and the k-particle contracted Schrödinger equations, CSEk. These conditions express the k-particle density matrices γk in terms of density matrices of higher particle rank. The latter can be eliminated if one expresses the γk in terms of their cumulants λk, but this is not sufficient to make the BCk or CSEk separable (extensive), i.e., they are not expressible in terms of only connected diagrams. However, in a formulation based on the recently introduced general normal ordering with respect to arbitrary wave functions, the irreducible counterparts IBCk and ICSEk of the BCk and CSEk can be defined. They are easily evaluated explicitly in terms of the generalized Wick theorem for arbitrary wave functions, and they lead to equations for the direct construction of the cumulants λk, which are additively separable quantities and which scale linearly with the system size. The IBCk or the ICSEk are necessary conditions for γ and the λk to represent an exact n-fermionic eigenstate of the given Hamiltonian. To specify the desired state, additional conditions must be satisfied as well, e.g., the partial trace relations which relate λ2 to γ and γ2. The particle number and the total spin must be specified and n-representability conditions enter implicitly. While the nondiagonal elements of γ and the λk are determined by the IBCk or the ICSEk, the additional conditions mainly serve to fix the diagonal elements. A hierarchy of k-particle approximations is defined. It is based on the fact that the expansion in terms of cumulants λk can be truncated at any particle rank, which would not be possible for the density matrices γk. For closed-shell states the one-particle approximation agrees with Hartree–Fock.

The Journal of Chemical Physics•Feb 1, 2001•106 citations

Quantum chemistry in Fock space. III. Particle-hole formalism

Werner Kutzelnigg

A particle-hole formalism is defined which is consistent with the tensor notation (and the index pairing) of the generators of the unitary group and their many-particle generalization. The corresponding generalized Wick theorem is formulated. The classification of basis operators as ‘‘closed,’’ ‘‘open,’’ ‘‘closed from above,’’ and ‘‘closed from below’’ given previously is extended to the present context. Both the perturbative and nonperturbative construction of effective Fock space Hamiltonians is discussed in the particle-hole formalism, especially for the case that the ‘‘physical vacuum’’ satisfies a Hartree–Fock condition. For the calculations of the correlation energy of the physical vacuum Cizek’s CP-MET is compared formally with the unitary variant, the UNICEP (unitary coupled electron pair) approximation. A simple derivation of Goldstone’s ‘‘linked-cluster expansion’’ is also given.

The Journal of Chemical Physics•Jan 15, 1984•172 citations

Cumulant decomposition of reduced density matrices, multireference normal ordering, and Wicks theorem: A spin-free approach

K. R. Shamasundar

We propose a spin-free approach to the cumulant decomposition of reduced density matrices of singlet and spin-rotation or SU(2) invariant ensemble of nonsinglet states as in [W. Kutzelnigg and D. Mukherjee, J. Chem. Phys. 110, 2800 (1999); 116, 4787 (2002)]. We provide a simple recursive procedure to obtain expressions which relate different spin components of spin-orbital reduced density matrices and cumulants of such states to the spin-free counterparts. These results are used to set up a spin-summation procedure to arrive at a definition of spin-free cumulants of any order. Alternatively, an analytic formula for the spin-free form resulting from a spin summation involving product of two spin-orbital cumulants is derived and its utility in spin-free cumulant decomposition of reduced density matrices is demonstrated. This leads to suitable definitions of spin-free analog of multireference normal ordering and the associated Wicks theorem. The results of this formulation are expected to be useful in investigations of spin-free multireference internally contracted coupled-cluster methods where cumulant approximations to the active reduced density matrices are employed.

The Journal of Chemical Physics•Nov 4, 2009•49 citations

Spinfree formulation of reduced density matrices, density cumulants and generalised normal ordering

Werner Kutzelnigg, K. R. Shamasundar, Debashis Mukherjee

The k-particle reduced density matrices γ k for a singlet state or a spin-orientation averaged ensemble are invariant under the spin rotation group SU(2), i.e. they are independent of spin, even if they are expressed in terms of spin orbitals. The γ k contain the same information as their spinfree counterparts Γ k expressed in terms of spinfree orbitals. However, the relation between the two quantities is, by no means, elementary. The summation over spin is particularly demanding and surprisingly complicated for the k-particle density cumulants λ k and for the formulation of a generalised normal ordering with respect to an arbitrary reference state, including the generalised Wick theorem. Plausible extrapolations from small k turned out to be unjustified and some published expressions for k = 4 need to be revised. A compact general result, valid for all k has not yet been found.

Molecular Physics•Feb 10, 2010•54 citations

Automatic derivation of many-body theories based on general Fermi vacua

Francesco A. Evangelista

This paper describes Wick&d, an implementation of the algebra of second-quantized operators normal ordered with respect to general correlated references and the corresponding Wick theorem [D. Mukherjee, Chem. Phys. Lett. 274, 561 (1997) and W. Kutzelnigg and D. Mukherjee, J. Chem. Phys. 107, 432 (1997)]. Wick&d employs a compact representation of operators and a backtracking algorithm to efficiently evaluate Wick contractions. Since Wick&d can handle both fully and partially contracted terms, it can be applied to both projective and Fock-space many-body formalisms. To demonstrate the usefulness of Wick&d, we use it to evaluate the single-reference coupled cluster equations up to octuple excitations and report an automated derivation and implementation of the second-order driven similarity renormalization group multireference perturbation theory.

arXiv:2205.01178•The Journal of Chemical Physics•Aug 12, 2022•24 citations

Canonical perturbation theory for nonlinear systems

Hajo Leschke, Allen C. Hirshfeld, Tsuneo Suzuki

We study perturbation expansions for quantum systems which are nonlinear in the sense that they may contain derivative couplings. The characteristic feature of these systems is the occurrence of products of noncommuting operators in the interaction Hamiltonian. In order to perform perturbation expansions in the Dyson-Wick manner it is in general necessary to order these operators according to some ordering scheme. We determine the most general scheme of this sort which allows a Dyson-Wick expansion with pair contractions. It involves a set $\ensuremath{\lambda}$ of three dimensionless ordering parameters which are related to the three $a$ priori undetermined equal-time contractions. Different $\ensuremath{\lambda}$-ordering schemes are related via an "equal-time" or "static" Wick theorem. In order to be able to contract operators which may be taken either at equal or at different times we introduce a time-ordering operation ${T}_{\ensuremath{\lambda}}$ which extends Dyson's time-ordering operation to equal times in a fashion dependent on the $\ensuremath{\lambda}$ ordering. We arrive at a "dynamic" Wick theorem which enables us to decompose the ${T}_{\ensuremath{\lambda}}$ product of a set of operators taken at arbitrary times into a sum of ${\ensuremath{\lambda}}^{\ensuremath{'}}$ products, where the most important case is that in which ${\ensuremath{\lambda}}^{\ensuremath{'}}$ represents normal ordering. Contrary to the usual Wick theorem ours works also in the case when two or more times coincide. Applying this theorem to the scattering operator expressed as a ${T}_{\ensuremath{\lambda}}$ product we obtain a class of Dyson-Wick expansions for nonlinear systems. Different expansions correspond to different choices of the ordering $\ensuremath{\lambda}$ and lead to different Feynman rules. The resulting diagrammatic technique for nonlinear systems is seen to have the following special features: (i) The interaction vertices include terms which arise from "quantum corrections," which are dependent on the ordering \ensuremath{\lambda} chosen for the noncommuting factors in the interaction Hamiltonian, and (ii) the equal-time contractions which occur in the closed-loop diagrams must be assigned corresponding $\ensuremath{\lambda}$-dependent values. In this way individual diagrams are $\ensuremath{\lambda}$ dependent. Nevertheless their sum is $\ensuremath{\lambda}$ independent, confirming the fact that the complete scattering operator is independent of the particular ordering chosen. The ordering multiplicity is also reflected in functional versions of the Dyson-Wick expansion. In the path-integral version this multiplicity lurks in the different possible discretization prescriptions. We discuss the relevance of our considerations to the question of the invariance of a quantum theory with respect to nonlinear point transformations. For the special case of a reducible system we present explicit calculations which show how this invariance is maintained in perturbation theory, for any ordering scheme belonging to the $\ensuremath{\lambda}$ class. In any particular scheme the invariance is ensured by a more or less intricate cancellation mechanism between the individual diagrams.

Physical review. D. Particles, fields, gravitation, and cosmology/Physical review. D. Particles and fields•Oct 15, 1978•24 citations
A generalization of normal ordering and of Wick’s theorem with respect to an arbitrary reference function Φ as some generalized “physical vacuum” is formulated in a different (but essentially equivalent) way than that suggested previously by one of the present authors. Guiding principles are that normal order operators with respect to any reference state must be expressible as linear combinations of those with respect to the genuine vacuum, that the vacuum expectation value of a normal order operator must vanish (with respect to the vacuum to which it is in normal order), and that the well-known formalism for a single Slater determinant as physical vacuum must be contained as a special case. The derivation is largely based on the concepts of “Quantum Chemistry in Fock space,” which means that particle-number-conserving operators (excitation operators) play a central role. Nevertheless, the contraction rules in the frame of a generalized Wick theorem are derived, that hold for non-particle-number-conserving operators as well. The contraction rules are formulated and illustrated in terms of diagrams. The contractions involve the “residual n-particle density matrices” λ, which are the irreducible (non-factorizable) parts of the conventional n-particle density matrices γ, in the sense of a cumulant expansion for the density. A spinfree formulation is presented as well. The expression of the Hamiltonian in normal order with respect to a multiconfiguration reference function leads to a natural definition of a generalized Fock operator. MC-SCF-theory is easily worked out in this context. The paper concludes with a discussion of the excited configurations and the first-order interacting space, that underlies a perturbative coupled cluster type correction to the MCSCF function for an arbitrary reference function, and with general implications of the new formalism, that is related to “internally contracted multireference configuration interaction.” The present generalization of normal ordering is not only valid for arbitrary reference functions, but also if the reference state is an ensemble state.
Two alternative conditions for the stationarity of the energy expectation value with respect to k-particle excitations are the k-particle Brillouin conditions BCk and the k-particle contracted Schrödinger equations, CSEk. These conditions express the k-particle density matrices γk in terms of density matrices of higher particle rank. The latter can be eliminated if one expresses the γk in terms of their cumulants λk, but this is not sufficient to make the BCk or CSEk separable (extensive), i.e., they are not expressible in terms of only connected diagrams. However, in a formulation based on the recently introduced general normal ordering with respect to arbitrary wave functions, the irreducible counterparts IBCk and ICSEk of the BCk and CSEk can be defined. They are easily evaluated explicitly in terms of the generalized Wick theorem for arbitrary wave functions, and they lead to equations for the direct construction of the cumulants λk, which are additively separable quantities and which scale linearly with the system size. The IBCk or the ICSEk are necessary conditions for γ and the λk to represent an exact n-fermionic eigenstate of the given Hamiltonian. To specify the desired state, additional conditions must be satisfied as well, e.g., the partial trace relations which relate λ2 to γ and γ2. The particle number and the total spin must be specified and n-representability conditions enter implicitly. While the nondiagonal elements of γ and the λk are determined by the IBCk or the ICSEk, the additional conditions mainly serve to fix the diagonal elements. A hierarchy of k-particle approximations is defined. It is based on the fact that the expansion in terms of cumulants λk can be truncated at any particle rank, which would not be possible for the density matrices γk. For closed-shell states the one-particle approximation agrees with Hartree–Fock.
A particle-hole formalism is defined which is consistent with the tensor notation (and the index pairing) of the generators of the unitary group and their many-particle generalization. The corresponding generalized Wick theorem is formulated. The classification of basis operators as ‘‘closed,’’ ‘‘open,’’ ‘‘closed from above,’’ and ‘‘closed from below’’ given previously is extended to the present context. Both the perturbative and nonperturbative construction of effective Fock space Hamiltonians is discussed in the particle-hole formalism, especially for the case that the ‘‘physical vacuum’’ satisfies a Hartree–Fock condition. For the calculations of the correlation energy of the physical vacuum Cizek’s CP-MET is compared formally with the unitary variant, the UNICEP (unitary coupled electron pair) approximation. A simple derivation of Goldstone’s ‘‘linked-cluster expansion’’ is also given.
We propose a spin-free approach to the cumulant decomposition of reduced density matrices of singlet and spin-rotation or SU(2) invariant ensemble of nonsinglet states as in [W. Kutzelnigg and D. Mukherjee, J. Chem. Phys. 110, 2800 (1999); 116, 4787 (2002)]. We provide a simple recursive procedure to obtain expressions which relate different spin components of spin-orbital reduced density matrices and cumulants of such states to the spin-free counterparts. These results are used to set up a spin-summation procedure to arrive at a definition of spin-free cumulants of any order. Alternatively, an analytic formula for the spin-free form resulting from a spin summation involving product of two spin-orbital cumulants is derived and its utility in spin-free cumulant decomposition of reduced density matrices is demonstrated. This leads to suitable definitions of spin-free analog of multireference normal ordering and the associated Wicks theorem. The results of this formulation are expected to be useful in investigations of spin-free multireference internally contracted coupled-cluster methods where cumulant approximations to the active reduced density matrices are employed.
The k-particle reduced density matrices γ k for a singlet state or a spin-orientation averaged ensemble are invariant under the spin rotation group SU(2), i.e. they are independent of spin, even if they are expressed in terms of spin orbitals. The γ k contain the same information as their spinfree counterparts Γ k expressed in terms of spinfree orbitals. However, the relation between the two quantities is, by no means, elementary. The summation over spin is particularly demanding and surprisingly complicated for the k-particle density cumulants λ k and for the formulation of a generalised normal ordering with respect to an arbitrary reference state, including the generalised Wick theorem. Plausible extrapolations from small k turned out to be unjustified and some published expressions for k = 4 need to be revised. A compact general result, valid for all k has not yet been found.
This paper describes Wick&d, an implementation of the algebra of second-quantized operators normal ordered with respect to general correlated references and the corresponding Wick theorem [D. Mukherjee, Chem. Phys. Lett. 274, 561 (1997) and W. Kutzelnigg and D. Mukherjee, J. Chem. Phys. 107, 432 (1997)]. Wick&d employs a compact representation of operators and a backtracking algorithm to efficiently evaluate Wick contractions. Since Wick&d can handle both fully and partially contracted terms, it can be applied to both projective and Fock-space many-body formalisms. To demonstrate the usefulness of Wick&d, we use it to evaluate the single-reference coupled cluster equations up to octuple excitations and report an automated derivation and implementation of the second-order driven similarity renormalization group multireference perturbation theory.
We study perturbation expansions for quantum systems which are nonlinear in the sense that they may contain derivative couplings. The characteristic feature of these systems is the occurrence of products of noncommuting operators in the interaction Hamiltonian. In order to perform perturbation expansions in the Dyson-Wick manner it is in general necessary to order these operators according to some ordering scheme. We determine the most general scheme of this sort which allows a Dyson-Wick expansion with pair contractions. It involves a set $\ensuremath{\lambda}$ of three dimensionless ordering parameters which are related to the three aaa priori undetermined equal-time contractions. Different $\ensuremath{\lambda}$-ordering schemes are related via an "equal-time" or "static" Wick theorem. In order to be able to contract operators which may be taken either at equal or at different times we introduce a time-ordering operation ${T}_{\ensuremath{\lambda}}$ which extends Dyson's time-ordering operation to equal times in a fashion dependent on the $\ensuremath{\lambda}$ ordering. We arrive at a "dynamic" Wick theorem which enables us to decompose the ${T}_{\ensuremath{\lambda}}$ product of a set of operators taken at arbitrary times into a sum of ${\ensuremath{\lambda}}^{\ensuremath{'}}$ products, where the most important case is that in which ${\ensuremath{\lambda}}^{\ensuremath{'}}$ represents normal ordering. Contrary to the usual Wick theorem ours works also in the case when two or more times coincide. Applying this theorem to the scattering operator expressed as a ${T}_{\ensuremath{\lambda}}$ product we obtain a class of Dyson-Wick expansions for nonlinear systems. Different expansions correspond to different choices of the ordering $\ensuremath{\lambda}$ and lead to different Feynman rules. The resulting diagrammatic technique for nonlinear systems is seen to have the following special features: (i) The interaction vertices include terms which arise from "quantum corrections," which are dependent on the ordering \ensuremath{\lambda} chosen for the noncommuting factors in the interaction Hamiltonian, and (ii) the equal-time contractions which occur in the closed-loop diagrams must be assigned corresponding $\ensuremath{\lambda}$-dependent values. In this way individual diagrams are $\ensuremath{\lambda}$ dependent. Nevertheless their sum is $\ensuremath{\lambda}$ independent, confirming the fact that the complete scattering operator is independent of the particular ordering chosen. The ordering multiplicity is also reflected in functional versions of the Dyson-Wick expansion. In the path-integral version this multiplicity lurks in the different possible discretization prescriptions. We discuss the relevance of our considerations to the question of the invariance of a quantum theory with respect to nonlinear point transformations. For the special case of a reducible system we present explicit calculations which show how this invariance is maintained in perturbation theory, for any ordering scheme belonging to the $\ensuremath{\lambda}$ class. In any particular scheme the invariance is ensured by a more or less intricate cancellation mechanism between the individual diagrams.