State independence commutation relations, effective

Appendix E Preservation of Commutation Relations by State-Independent Effective Operator Definitions Other than A Acknowledgments References... 

The effective operator A is the state-independent part of the definition AL/3, i = I-III. The operator A can thus be obtained by combining the perturbation expansions of its normalization factors and of A into a single expression [73] or by computing these normalization factors and A separately. These combined and noncombined forms of A[, may differ when computed approximately (see Section VI and paper II). The calculation of with the noncombined form is the same as with A since the model eigenvectors used with A are obtained by multiplying those utilized with A[,p by the above normalization factors. The operators and A are nevertheless different and, thus, do not have necessarily the same properties, for example, the conservation of commutation relations studied in Section IV. 

This section studies the previously unaddressed problem of commutation relation conservation upon transformation to effective operators [77]. State-independent effective operators are treated first. 

Section II and Table I show that state-independent effective operators can be obtained with norm-preserving mappings K, or with any of the three kinds of non-norm-preserving mappings K, L), K, L), and K, L). This section first proves that the commutation relations between two arbitrary operators cannot generally be conserved upon transformation to any of these state-independent effective operators. A determination is then made of operators whose commutation relations are preserved by at least some state-independent effective operator definitions, and a few applications are then presented. Particular interest is focused on operators which commute with H, including constants of the motion. 

Theorem IV pertains to commutation relations for all possible state-independent effective operators Let A and B be two arbitrary operators and let F be their commutator F = [A,B. The commutation relation between A and B is, in general, not conserved upon transformation to state-independent effective operators. This theorem is first demonstrated... 

We now determine particular classes of commutation relations that are, indeed, conserved upon transformation to state-independent effective operators. The proof of (4.1) demonstrates that the preservation of [A, B] by definition A requires the existence of a relation between K, K, or both and one or both of the true operators A or B. Likewise, there must be a relation between the appropriate wave operator, the inverse mapping operator, or both, and A, B, or both for other state-independent effective operator definitions to conserve [A, B]. All mapping operators depend on the spaces and fl. Although the model space is often specified by selecting eigenfunctions of a zeroth order Hamiltonian, it may, in principle, be arbitrarily defined. On the other hand, the space fl necessarily depends on H. Therefore, the existence of a relation between mapping operators and A, B, or both, implies a relation between H and A, B, or both. 

The key step in deriving (4.7) is the commutation of P with H. Clearly, a similar reasoning applies when replacing H with any operator that commutes with H because such an operator also commutes with P. Therefore, this leads to Theorem V as follows state-independent effective operators produced by norm-preserving mappings conserve the commutation relations between H and an arbitrary operator B and between B and any operator that commutes with H. Given particular choices of P,... 

Hence, the commutation relation between A and B is conserved iff the right hand sides of Eqs. (4.8) and (4.9) are equal to each other, thereby leading to Theorem VII as follows the commutation relation between two operators A and B is preserved upon transformation to state-independent effective operators obtained with norm-preserving mappings iff A and B satisfy... 

The commutation relation between two arbitrary operators is not conserved upon transformation to effective operators by any of the definitions. Many state-independent effective operator definitions preserve the commutation relations involving // or a constant of the motion, as well as those involving operators which are related to P in a special way, for example, A with [P, 4] = 0. Many state-dependent definitions also conserve these special commutation relations. However, state-dependent definitions are not as convenient for formal and possibly computational reasons. The most important preserved commutation relations are those involving observables, since, as discussed in Section VII, they ensure that the basic symmetries of the system are conserved in effective Hamiltonian calculations. 

Semi-empirical Hamiltonians and operators are taken to be state independent [56] and have the same Hermiticity as their true counterparts. Consequently, the valence shell effective Hamiltonians and operators they mimic must also have these two properties. Table I shows that the effective Hani iltonian and operator definitions H and A, as well as H and either A or a fulfill these criteria. Thus, these definition pairs may be used to derive the valence shell effective Hamiltonians and operators mimicked by the semi-empirical methods. Table III indicates that the commutation relation (4.12) is preserved by all three definition pairs. Hence, the validity of the relations derived from the semi-empirical version of (4.12) depends on the extent to which the semi-empirical Hamiltonians and operators actually mimic, respectively, exact valence shell effective Hamiltonians and operators. In particular, the latter Hamiltonians and operators contain higher-body terms which are neglected, or ignored, in semi-empirical theories. These nonclassical higher body interactions have been shown to be nonnegligible for the valence shell Hamiltonians of many atoms and molecules [27, 145-149] and for the dipole moment operators of some small molecules [56-58]. There is no a... 

APPENDIX E PRESERVATION OF COMMUTATION RELATIONS BY STATE-INDEPENDENT EFFECTIVE OPERATOR DEFINITIONS OTHER THAN A... 

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