Elementary properties of an energy functional of the first-order reduced density matrix

Abstract

The Hohenberg–Kohn theorem implies the existence of an energy functional based solely on the first-order reduced density matrix of the ground state of an atomic or molecular system. Application of the variational principle for the functional EvM[γ] generates a set of coupled Euler equations for the representation coefficients and spin orbitals of a rank-M approximation to the exact ground-state density matrix. Defining the (assumed Hermitian) kernel FM[γ;x′,x]≡δEvM/δγ (x,x′), the equations in an arbitrary representation for the approximate density matrix, γ (x,x′) =ΣijMψ1(x) γijψj* (x′) are the following: ℱdξFM[γ;x′,ξ]ψi(ξ) =μψi(x′); i=1, 2,...,M; ℱdξFM[γ;x′,ξ] ΣMiψi(ξ) γ ij=ΣMiψi(x′) λij; j=1, 2, ...,M. The quantity μ is the chemical potential of the system of interest and the λij are a set of M2 Lagrange multipliers constraining the orthonormality of the spin orbital basis {ψ}. The coefficients γij must be chosen such that FM has the degenerate eigenvalue spectrum, FiiM=μ, i=1, 2,...,M, for all partially occupied orbitals. The spin orbitals, for a fixed set of coefficients, must be simultaneously determined so that λ is Hermitian. Provided all occupation numbers lie on the open interval (0,1), the stationary density matrix itself obeys the eigenvalue equation ℱdξFM[γ;x,ξ]γ (ξ,x′) =μγ (x,x′), and for any stationary density matrix the following commutation rules are valid: [FM[γ], γ]=0; [λ, γ]=0. The matrices γ and λ consequently can be brought simultaneously to diagonal form, and the canonical representation of the energy functional provides an eigenvalue equation determining the natural spin orbitals. The value of the chemical potential is μ=εi/ni, i=1, 2, ...,M; ε=diag (λ); from which follows the distribution function governing the occupation numbers of a stationary density matrix. Two limiting forms of the variational principle are examined, the exact and Hartree–Fock functionals, and related previous work by Gilbert is discussed. The physical content of the equations is illuminated by identification of the chemical potential as the negative of the electronegativity; Sanderson’s Principle of Electronegativity Equalization follows.

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

“…By expanding the system's energy, E, in a secondorder Taylor series with respect to these variables, a number of sensitivities can be defined. They include the global chemical potential of electrons (l) [44], the global hardness (g) [45], polarization/linear response kernel (b) [46] and Fukui function (f(r)) [47]. Chemical potential l measures the leaving tendency of electrons in the system.…”

Circulant orbitals for atoms and molecules

“…2 and 4. Canonical or spectroscopic orbitals are orbitals XA that diagonalize E, FAe = AfE (AkIlIAd = SkfEf [6] The "orbital energies" Ee are excellent approximations to ionization potentials, but for the description of the system of interest there is no inherent reason to prefer the orbitals Ae to [1] other choices or orbitals. Eqs.…”

“…Circulant orbitals themselves should be extremely useful in studying the transition between and relations among orbital theories and density functional theories of electronic structure of atoms and molecules (5,6).…”

Perspective on natural orbital functional theory

“…In 1974, Gilbert proved the analog of the Hohenberg-Kohn (HK) theorem for the one-particle reduced density matrix (1-RDM), C. [1] The existence of the 1-RDM functional was already implicit in the original HK theorem, [2] but the most elegant proof of it was probably provided by Levy. [3] A major advantage of the 1-RDM theory is that the kinetic energy is explicitly defined in terms of C and hence, do not require the construction of an approximate functional.…”