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arXiv:2101.10944 · The Journal of Chemical Physics

Generalized nonorthogonal matrix elements: Unifying Wick’s theorem and the Slater–Condon rules

Hugh G. A. Burton

Published Apr 13, 2021• 28 citations

Abstract

Matrix elements between nonorthogonal Slater determinants represent an essential component of many emerging electronic structure methods. However, evaluating nonorthogonal matrix elements is conceptually and computationally harder than their orthogonal counterparts. While several different approaches have been developed, these are predominantly derived from the first-quantized generalized Slater-Condon rules and usually require biorthogonal occupied orbitals to be computed for each matrix element. For coupling terms between nonorthogonal excited configurations, a second-quantized approach such as the nonorthogonal Wick's theorem is more desirable, but this fails when the two reference determinants have a zero many-body overlap. In this contribution, we derive an entirely generalized extension to the nonorthogonal Wick's theorem that is applicable to all pairs of determinants with nonorthogonal orbitals. Our approach creates a universal methodology for evaluating any nonorthogonal matrix element and allows Wick's theorem and the generalized Slater-Condon rules to be unified for the first time. Furthermore, we present a simple well-defined protocol for deriving arbitrary coupling terms between nonorthogonal excited configurations. In the case of overlap and one-body operators, this protocol recovers efficient formulas with reduced scaling, promising significant computational acceleration for methods that rely on such terms.

DOI: 10.1063/5.0045442

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Matrix elements between nonorthogonal Slater determinants represent an essential component of many emerging electronic structure methods. However, evaluating nonorthogonal matrix elements is conceptually and computationally harder than their orthogonal counterparts. While several different approaches have been developed, these are predominantly derived from the first-quantized generalized Slater-Condon rules and usually require biorthogonal occupied orbitals to be computed for each matrix element. For coupling terms between nonorthogonal excited configurations, a second-quantized approach such as the nonorthogonal Wick's theorem is more desirable, but this fails when the two reference determinants have a zero many-body overlap. In this contribution, we derive an entirely generalized extension to the nonorthogonal Wick's theorem that is applicable to all pairs of determinants with nonorthogonal orbitals. Our approach creates a universal methodology for evaluating any nonorthogonal matrix element and allows Wick's theorem and the generalized Slater-Condon rules to be unified for the first time. Furthermore, we present a simple well-defined protocol for deriving arbitrary coupling terms between nonorthogonal excited configurations. In the case of overlap and one-body operators, this protocol recovers efficient formulas with reduced scaling, promising significant computational acceleration for methods that rely on such terms.

In this series, the n-body reduced density matrix (n-RDM) approach for nonorthogonal orbitals and their applications to ab initio valence bond (VB) methods are presented. As the first paper of this series, Hamiltonian matrix elements between internally contracted VB wave functions are explicitly provided by means of nonorthogonal orbital based RDM approach. To this end, a more generalized Wick's theorem, called enhanced Wick's theorem, is presented both in arithmetical and in graphical forms, by which the deduction of expressions for the matrix elements between internally contracted VB wave functions is dramatically simplified, and the matrix elements are finally expressed in terms of tensor contractions of electronic integrals and n-RDMs of the reference VB self-consistent field wave function. A string-based algorithm is developed for the purpose of evaluating n-RDMs in an efficient way. Using the techniques presented in this paper, one is able to develop new methods and efficient algorithms for nonorthogonal orbital based many-electron theory much easier than by use of the first quantized formulism.

Numerical difficulties associated with computing matrix elements of operators between Hartree-Fock-Bogoliubov (HFB) wavefunctions have plagued the development of HFB-based many-body theories for decades. The problem arises from divisions by zero in the standard formulation of the nonorthogonal Wick's theorem in the limit of vanishing HFB overlap. In this Communication, we present a robust formulation of Wick's theorem that stays well-behaved regardless of whether the HFB states are orthogonal or not. This new formulation ensures cancellation between the zeros of the overlap and the poles of the Pfaffian, which appears naturally in fermionic systems. Our formula explicitly eliminates self-interaction, which otherwise causes additional numerical challenges. A computationally efficient version of our formalism enables robust symmetry-projected HFB calculations with the same computational cost as mean-field theories. Moreover, we avoid potentially diverging normalization factors by introducing a robust normalization procedure. The resulting formalism treats even and odd number of particles on equal footing and reduces to Hartree-Fock as a natural limit. As proof of concept, we present a numerically stable and accurate solution to a Jordan-Wigner-transformed Hamiltonian, whose singularities motivated the present work. Our robust formulation of Wick's theorem is a most promising development for methods using quasiparticle vacuum states.

The matrix element of a general many-body operator between two Slater determinants is calculated explicitly. For this, a split-and-pair method is introduced that provides a convenient expression of Wick's theorem and simplifies many-body calculations. The same method is used to determine the generating function of the matrix elements of many-body operators. The split-and-pair method allows also for the diagonalization of the density correlation operators $:n({x}_{1})\ensuremath{\cdots}n({x}_{k}):$, where $n(x)={\ensuremath{\psi}}^{\ifmmode\dagger\else\textdagger\fi{}}(x)\ensuremath{\psi}(x)$ is the density operator. The relation between the split-and-pair method and quantum group theory is clarified.

The Schmidt decomposition of quantum many-body states, which is the basis of many powerful quantum many-body techniques, relies on a partition of the whole system in terms of orthogonal local basis functions. We propose in this Letter a nonorthogonal decomposition of Slater determinants, which reduces to the conventional Schmidt decomposition in the orthogonal limit. The new decomposition provides a natural tool for building local correlation spaces when the orbitals are overlapping, which can be used to extend some existing embedding methods based on the Schmidt decomposition like density matrix embedding theory (DMET) to overlapping subsystem partitions to achieve greater flexibility and efficiency. We also propose a new quantum embedding strategy that bridges the ab initio model potential (AIMP) embedding and DMET, which circumvents the necessarity of a mean-field calculation of the whole system like AIMP, and is able to capture quantum entanglement like DMET.

Wick's theorem for the expectation value of an operator between many-particle states is generalized to the case of a homogeneous linear transformation operator

\^O

, which leaves invariant the

2N

-dimensional linear space composed of the annihilation and the creation operators for the N fermion or boson single-particle basis. Such a transformation generally belongs to the group

\mathrm{SO}(2N,C)

for the case of fermion, or the group

\mathrm{Sp}(2N,C)

for the case of boson. This theorem is applied to derive a reduction theorem for the matrix element of the type $〈\ensuremath{\alpha}|{\ensuremath{\alpha}}_{1}{\ensuremath{\alpha}}_{2}\ensuremath{\cdot}\ensuremath{\cdot}\ensuremath{\cdot}{\ensuremath{\alpha}}_{m}\^O{\ensuremath{\beta}}_{m+1}^{\ifmmode\dagger\else\textdagger\fi{}}{\ensuremath{\beta}}_{m+2}^{\ifmmode\dagger\else\textdagger\fi{}}\ensuremath{\cdot}\ensuremath{\cdot}\ensuremath{\cdot}{\ensuremath{\beta}}_{2n}^{\ifmmode\dagger\else\textdagger\fi{}}|\ensuremath{\beta}〉,$ whose many-quasiparticle states and vacua appearing in both sides are represented in different quasiparticle pictures as indicated by $\ensuremath{\alpha}$ and $\ensuremath{\beta}.$ The reduction formula is useful in calculating any nuclear transition matrix element for the quantum-number projection calculation associated with the constrained Hartree-Fock-Bogoliubov solutions, and also the generator coordinate method with quantum number projection.