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Spin-free quantum chemistry: What one can gain from fock's cyclic symmetry



The spin-free wave function due to Fock (Zh Eksp Teor Fiz, 1940, 10, 961) is re-examined with a stress on the reduced density matrix (RDM) theory. The key notion of the Fock approach is the cyclic symmetry of wave functions. It is a specific algebraic identity involving transpositions of numbers taken from two different columns of the corresponding Young tableau. We show first how to construct symmetry adapted states by accounting for high-order cyclic symmetry conditions. For Young's projectors, it gives a new expression including nothing but antisymmetrizers. Next, transforming the Fock spin-free state by a duality operator (the star operator in exterior algebra), we arrive at the representation closely related to spin-flip models. In such spin-flip models, a coupling operator is the basic object for which we show that the cyclic symmetry is transformed into a tracelessness of the coupling operator. The main results are related to the spin-free theory of spin properties. In particular, the theorem previously stated (Luzanov and Whyman, Int J Quantum Chem, 1981, 20, 1179) is refined by an explicit general representation of spin density operators through spin-free (charge) RDMs. Some applications implicating high-order RDMs (collectivity numbers, the unpaired electron problem, cumulant spin RDMs, spin correlators, etc.) are also considered. For spin-free RDM components, a new projection procedure without constructing any symmetry adapted state is proposed. An unsolved problem of constructing orthogonal representation matrices within the Fock theory is raised. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010