Annihilation operator, second quantization

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. 

In formulating the second-quantized description of a system of noninteracting fermions, we shall, therefore, have to introduce distinct creation and annihilation operators for particle and antiparticle. Furthermore, since all the fermions that have been discovered thus far obey the Pauli Exclusion principle we shall have to make sure that the formalism describes a many particle system in terms of properly antisymmetrized amplitudes so that the particles obey Fermi-Dirac statistics. For definiteness, we shall in the present section consider only the negaton-positon system, and call the negaton the particle and the positon the antiparticle. 

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 the usual formalism of quantum mechanics, the first quantization formalism, observables are represented by operators and the wave functions are normal functions. In the method of second quantization, the wave functions are also expressed in terms of operators. The formalism starts with the introduction of an abstract vector space, the Fock space. The basis vectors of the Fock space are occupation number vectors, with each vector defined by a set of occupation numbers (0 or 1 for fermions). An occupation number vector represents a Slater determinant with each occupation number giving the occupation of given spin orbital. Creation and annihilation operators that respectively adds and removes electrons are then introduced. Representations of usual operators are expressed in terms of the very same operators. 

Most formulations of MCSCF theory are based on the second quantization formalism. We therefore review briefly in this section the basic definitions of the annihilation and creation operators, and the expansion of quantum mechanical operators in products of them. 

Second-quantization formalism was introduced into the theory of many-electron atoms by Judd [12]. This formalism enables one to give a simple and elegant description of both the rotation symmetry of a system and its permutational symmetry the tensorial properties of wave functions are translated to electron creation and annihilation operators, and the Pauli exclusion principle stems automatically from the anticommutation relations between these operators. 

Second-quantization. Electron creation and annihilation operators... 

The pertinent transformation of the second-quantization operators now yields creation and annihilation operators for holes (13.34) and (13.35). 

In the second-quantization representation the atomic interaction operators are given by relations (13.22) and (13.23), which do not include the operators themselves in coordinate representations, but rather their one-electron and two-electron matrix elements. Therefore, in terms of irreducible tensors in orbital and spin spaces, we must expand the products of creation and annihilation operators that enter (13.22) and (13.23). In this approach, the tensorial properties of one-electron wave functions are translated to second-quantization operators. 

Utilization of the tensorial properties of the electron creation and annihilation operators allows us to obtain expansions in terms of irreducible tensors of any operators in the second-quantization representation. So, using the Wigner-Eckart theorem (5.15) in (14.11) and (14.12), then coupling ranks of second-quantization operators by (5.12) and utilizing (14.10), we can represent one-shell operators of angular momentum in the irreducible tensor form... 

Using second-quantization, it is often necessary to transform complicated tensorial products of creation and annihilation operators. If, to this end, conventional anticommutation relations (14.19) are used, then one proceeds as follows write the irreducible tensorial products in explicit form in terms of the sum over the projection parameters of conventional products of creation and annihilation operators, then place these operators in the required order, and finally sum the resultant expression again over the projection parameters. On the other hand, the use of (14.21) enables the irreducible tensorial products of second-quantization operators to be transformed directly. 

Let us now put (14.59) into the general formula (13.23) and rearrange the creation and annihilation operators so that when the second-quantization operators are placed side by side the rank projections enter into the same Clebsch-Gordan coefficient. A summation over the projections gives... 

The concept of quasispin quantum number was discussed in the Introduction and Chapter 9 (see formulas (9.22) and (9.23)). Now let us consider it in the framework of the second-quantization technique. We can introduce the following bilinear combinations of creation and annihilation operators obeying commutation relations (14.2) - the quasispin operator ... 

In Chapter 15, for the CFP with a detached electrons, we obtained a relationship (15.27) whose right side has the form of a vacuum average of a certain product of second-quantized operators q>. To obtain algebraic formulas for CFP, it is necessary to compute this vacuum average by transposing all the annihilation operators to the right side of the creation operators. So, for N = 3, we take into account (for non-repeating terms) the explicit form of operators (15.2) and (15.5), which produce pertinent wave functions out of vacuum, and find (cf. [107])... 

The relationships describing the tensorial properties of wave functions, second-quantization operators and matrix elements in the space of total angular momentum J can readily be obtained by the use of the results of Chapters 14 and 15 with the more or less trivial replacement of the ranks of the tensors l and s by j and the corresponding replacement of various factors and 3nj-coefficients. Therefore, we shall only give a sketch of the uses of the quasispin method for jj coupling, following mainly the works [30, 167, 168]. For a subshell of equivalent electrons, the creation and annihilation operators a and a(jf are the components of the same tensor of rank q = 1/2... 

A iV-electron vacancy (hole) in a shell may be denoted as nl N = ni4l+2-N (see aiso Chapters 9, 13 and 16). As we have seen in the second-quantization representation, symmetry between electrons and vacancies has deep meaning. Indeed, the electron annihilation operator at the same time is the vacancy creation operator and vice versa instead of particle representation hole (quasiparticle) representation may be used, etc. It is interesting to notice that the shift of energy of an electron A due to creation of a vacancy B l is approximately (usually with the accuracy of a few per cent) equal to the shift of the energy of an electron B due to creation of a vacancy A l, i.e. 

A very useful and convenient method that fulfils this postulate is the method of second quantization. That means, we describe all quantities (relevant for our system under consideration) in terms of so-called annihilation and creation operators a(b) and a+(b), respectively. 

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,... 

For applications the tunneling Hamiltonian (54) should be formulated in the second quantized form. We introduce creation and annihilation Schrodinger operators c fc, cRk, (hq, cRq. Using the usual rules we obtain... 

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 ... 

Hence the only term mixing electronic and nuclear coordinates is the second one in (A.2). We can now express it in a second quantization. If we consider one only mode of frequency f2, there is only one annihilation (creator) operator b (b+) for the mode. Thus,... 

This representation among others removes one more inconsistency in quantum chemistry one generally deals with the systems of constant composition i.e. of the fixed number of electrons. The expression eq. (1.178) allows one to express the matrix elements of an electronic Hamiltonian without the necessity to go in a subspace with number of electrons different from the considered number N which is implied by the second quantization formalism of the Fermi creation and annihilation operators and on the other hand allows to keep the general form independent explicitly neither on the above number of electrons nor on the total spin which are both condensed in the matrix form of the generators E specific for the Young pattern T for which they are calculated. 

The basic elements of the second-quantization formalism are the annihilation and creation operators (Linderberg and (3hrn, 1973). The annihilation operator ap annihilates an electron in orbital creation operator ap (the conjugate of ap) creates an electron in orbital p. These operators satisfy the anticommutation relations... 

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