The Hamiltonian in second quantization

Since the spectrum of the DCB Hamiltonian is not bounded from below it is not possible to optimize the wave function by minimization of the energy. The unphysical unboundedness is due to the fact that not all possible normalizible antisymmetric wave functions of N coordinates are states of an N-electron system. The set of possible solutions also contains wavefunctions in which one or more negative energy levels are occupied and it is the mixing with such states that gives rise to unphysical arbitrarily low energies. One needs the second quantization formalism of quantum electrodynamics (QED) for a proper treatment of these states. As this is discussed in more depth elsewhere in this 

The basic theory of second quantization is found in most advanced textbooks on quantum mechanics but inclusion of relativity is not often considered. A good introduction to this topic is given by Strange [10] in his recent textbook on relativistic quantum mechanics. We will basically follow his arguments but make the additional assumption that a finite basis of Im Kramers paired 4-spinors is used to expand the Dirac equation. This brings the formalism closer to quantum chemistry where use of an (infinite) basis of plane waves, as is done in traditional introductions to the subject, is impractical. 

Creation operators dj, and dl are defined to generate states with one electron in a positive 

Repeated application of the creation operators generates a Fock space in which many-particle states are expanded. Each of the basis states of this Fock space is represented by its occupation vector n given in the pair index notation 

All other operators can now be expressed as sums of products of matrix elements (complex numbers) with these creation or annihilation operators. The Dirac Hamiltonian becomes 

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It is easiest to see this relationship by writing the Hamiltonian in second quantized form ... 

Expressing the intermolecular direct Coulomb Hamiltonian in second quantization (as described in Section 2.6), namely,... 

Contents Introduction. - Concept of Creation and Annihilation Operators. -Particle Number Operators. - Second Quantized Representation of Quantum Mechanical Operators. - Evaluation of Matrix Elements. - Advantages of Second Quantization. - Illustrative Examples. - Density Matrices. -Connection to Bra and Ket Formalism. - Using Spatial Orbitals. - Some Model Hamiltonians in Second Quantized Form. - The Brillouin Theorem. -Many-Body Perturbation Theory. -Second Quantization for Nonorthogonal Orbitals. - Second Quantization and Hellmann-Feynman Theorem. - Inter-molecular Interactions. - Quasiparticle Transformations. Miscellaneous Topics Related to Second Quantization -Problem Solutions. - References -Index. 

These ideas can be applied to electrochemical reactions, treating the electrode as one of the reacting partners. There is, however, an important difference electrodes are electronic conductors and do not posses discrete electronic levels but electronic bands. In particular, metal electrodes, to which we restrict our subsequent treatment, have a wide band of states near the Fermi level. Thus, a model Hamiltonian for electron transfer must contains terms for an electronic level on the reactant, a band of states on the metal, and interaction terms. It can be conveniently written in second quantized form, as was first proposed by one of the authors [Schmickler, 1986] ... 

In (4.28) and (4.30), we have achieved our aim of expressing the Hamiltonian in the appropriate second quantized form for acting on the state vectors in Fock space. 

Recent application of the TB method to transition metal clusters often made use of a convenient formulation in the language of second quantization.14 In this formalism, the TB Hamiltonian in the unrestricted Hartree-Fock approximation can be written as a sum of diagonal and nondiagonal terms15... 

The very simplest theoretical approach, with linear electron-phonon coupling, is in terms of a two-center (a,b) one-electron Hamiltonian (27), with just one harmonic mode, u>, associated with each center. This is (in second quantized notation, with H = 1) ... 

The Dirac-Coulomb-Breit Hamiltonian rewritten in second-quantized... 

By Eq. (6) the sum on the right-hand side of the above equation is equal to the energy E, and from Eq. (2) we realize that the sums on the left-hand side are just Hamiltonian operators in the second-quantized notation. Hence, when the 2-RDM corresponds to an A -particle wavefunction i//, Eq. (12) implies Eq. (13), and the proof of Nakatsuji s theorem is accomplished. Because the Hamiltonian is dehned in second quantization, the proof of Nakatsuji s theorem is also valid when the one-particle basis set is incomplete. Recall that the SE with a second-quantized Hamiltonian corresponds to a Hamiltonian eigenvalue equation with the given one-particle basis. Unlike the SE, the CSE only requires the 2- and 4-RDMs in the given one-particle basis rather than the full A -particle wavefunction. While Nakatsuji s theorem holds for the 2,4-CSE, it is not valid for the 1,3-CSE. This foreshadows the advantage of reconstructing from the 2-RDM instead of the 1-RDM, which we will discuss in the context of Rosina s theorem. 

As shown in the second line, like the expression for the energy as a function of the 2-RDM, the energy E may also be expressed as a linear functional of the two-hole reduced density matrix (2-HRDM) and the two-hole reduced Hamiltonian K. Direct minimization of the energy to determine the 2-HRDM would require (r — A)-representability conditions. The definition for the p-hole reduced density matrices in second quantization is given by... 

The Dirac-Coulomb-Breit Hamiltonian H qb 1 rewritten in second-quantized form [6, 16] in terms of normal-ordered products of spinor creation and annihilation operators r+s and r+s+ut, ... 

In order to be able to write out all the terms of the direct Cl equations explicitly, the Hamiltonian operator is needed in a form where the integrals appear. This is done using the language of second quantization, which has been reviewed in the mathematical lectures. Since, in the MR-CI method, we will generally work with spin-adapted configurations a particularly useful form of the Hamiltonian is obtained in terms of the generators of the unitary group. The Hamiltonian in terms of these operators is written,... 

Operators corresponding to physical quantities, in second-quantization representation, are written in a very simple form. In the quantum mechanics of identical particles we normally have to deal with two types of operators symmetric in the coordinates of all particles. The first type includes N-particle operators that are the sum of one-particle operators. An example of such an operator is the Hamiltonian of a system of noninteracting electrons (e.g. the first two terms in (1.15)). The second type are iV-particle operators that are the sum of two-particle operators (e.g. the energy operator for the electrostatic interaction of electrons - the last term in (1.15)). In conventional representations these operators are... 

We now introduce creation and annihilation operators ajj and an which create/annihilate e-h pairs at a given combination of sites n = (n, n1), i.e., 41°) = 14 = nen h), where 0) is the ground state. Using these operators, a generic monoexcitation configuration interaction Hamiltonian can be formulated as follows in second quantization notation,... 

One of the most important concepts of quantum chemistry is the Slater determinant. Most quantum chemical treatments are made just over Slater determinants. Nevertheless, in many problems the formulation over Slater determinants is not very convenient and the derivation of final expressions is very complicated. The advantage of second quantization lies in the fact that this technique permits us to arrive at the same expressions in a considerably simpler way. In second quantization a Slater determinant is represented by a product of creation and annihilation operators. As will be shown below, the Hamiltonian can also be expressed by creation and annihilation operators and thus the eigenvalue problem is reduced to the manipulation of creation and annihilation operators. This manipulation can be done diagrammatically (according to certain rules which will be specified later) and from the diagrams formed one can write down the final mathematical expression. In the traditional way a Slater determinant I ) is specified by one-electron functions as follows ... 

Wick s theorem (35) which gives us the prescription for treating a product of operators may of course be applied to the Hamiltonian, expressed in the second quantization formalism (29). This leads to the Hamiltonian in a form which is of primary importance in perturbation treatments. This form of the Hamiltonian which is called the normal product form is ... 

H is the Hamiltonian operator expressed in the language of second quantization,... 

The PPP Hamiltonian can then be written in second quantized form as... 

The total energy has an explicit geometry dependence in the nuclear-electron and nuclear-nuclear interaction terms, and an implicit geometry dependence in the wave function. In approximate calculations where finite nuclear-fixed basis sets are used, the total energy has an explicit dependence also in the basis set. Using the technique of second quantization, the geometry dependence of the basis set may be transferred to the Hamiltonian. In Section II we describe how the Hamiltonian at X0 + p may be expanded around X0... 

This general notation is deceptively simple. The bra is an excited determinant. There is an equation for each excited determinant, and each level of excitation leads to a different type of equation. Furthermore, the equations are all coupled, and they are non-linear in the amplitudes. However, they may be formulated in a quasilinear manner [27], and they have been solved for a wide range of CC schemes. The operator HN is the Hamiltonian written in second-quantized form minus the energy of the reference determinant, i.e. HN = H— < 0 /7 0 >. The subscript C restricts the operator product of HN and eT to connected terms. Once the CC equations have been solved, the CC correlation energy can be calculated from... 

The Hamiltonian in the second quantization directly includes the approximations... 

In this expression, hp = pW q) represeiits a matrix element of the one-electron component of the Hamiltonian, h, while (pqWrs) s ( lcontains general annihilation and creation operators (e.g., or ) that may act on orbitals in either occupied or virtual subspaces. The cluster operators, T , on the other hand, contain operators that are restricted to act in only one of these spaces (e.g., al, which may act only on the virtual orbitals). As pointed out earlier, the cluster operators therefore commute with one another, but not with the Hamiltonian, f . For example, consider the commutator of the pair of general second-quantized operators from the one-electron component of the Hamiltonian in Eq. [53] with the single-excitation pair found in the cluster operator, Tj ... 

Here II (l) corresponds to the part of the energy that depends on the configuration of the Zth proton, and Hiijl) is the part of the energy that depends on the pair configuration of the Zth and the jth protons. It is assumed that protons tunnel between two equilibrium positions (hence the double-well potential should be symmetric). In the presentation of second quantization in which the one-particle Hamiltonian Hi (Z) is diagonalized, the total Hamiltonian is written as... 

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