Electron density matrix elements transferability

It is interesting to compare the possibilities and errors of different hybrid QM/MM schemes. The careful examination and comparison of link atom and LSCF techniques was performed in Ref. [128] using the CHARMM force field [114] and the AMI method [143] as a quantum chemical procedure. In the case of the link atom procedure two options were used QQ - the link atom does not interact with the MM subsystem and HQ - link atom interacts with all MM atoms. The main conclusion of this consideration is that the LSCF and the link atom schemes are of similar quality. The error in the proton affinity determination induced by these schemes is several kcal/mol. It is noteworthy that all the schemes work rather badly in description of conformational properties of n-butane. The large charge on the MM atoms in the proximity of the QM subsystem (especially on the boundary atom) cause significant errors in the proton affinity estimates for all methods (especially, in the case of the LSCF approach where the error can be of tens of kcal/mol). This is not surprising since the stability and transferability of intrabond one- and two-electron density matrix elements Eq. (19) is broken here. It proves that the simple electrostatic model is not well appropriate for these schemes and that a detailed analysis of the... 

The theory of the multi-vibrational electron transitions based on the adiabatic representation for the wave functions of the initial and final states is the subject of this chapter. Then, the matrix element for radiationless multi-vibrational electron transition is the product of the electron matrix element and the nuclear element. The presented theory is devoted to the calculation of the nuclear component of the transition probability. The different calculation methods developed in the pioneer works of S.I. Pekar, Huang Kun and A. Rhys, M. Lax, R. Kubo and Y. Toyozawa will be described including the operator method, the method of the moments, and density matrix method. In the description of the high-temperature limit of the general formula for the rate constant, specifically Marcus s formula, the concept of reorganization energy is introduced. The application of the theory to electron transfer reactions in polar media is described. Finally, the adiabatic transitions are discussed. 

The one-center energy components have no clear correspondence in the standard MM setting. In our approach the one-center contributions E- arise due to deviations of the geminal amplitude related ES Vs (7>P and 41 ) from their transferable values. These deviations interfere with hybridization. The derivatives of E f s with respect to the angles Land uji, taken at the values characteristic for the stable hybridization tetrahedra shapes which appear in the FATO model, yield quasi- and pseudotorques acting upon the hybridization tetrahedron. In evaluating these quantities we notice that all the hybridization dependence which appears in the one-center terms is that of the matrix elements of eq. (2.71). In the latter, the only source of the hybridization dependence is that of the second and fourth powers of the coefficients of the s-orbital in the HOs. Since they do not depend on the orientation of the hybridization tetrahedra, we immediately arrive at the conclusion that no quasitorques caused by the variation of electron densities appear in the TATO setting ... 

The RASSI method can be used to compute first and second order transition densities and can thus also be used to set up an Hamiltonian in a basis of RASSCF wave function with separately optimized MOs. Such calculations have, for example, been found to be useful in studies of electron-transfer reactions where solutions in a localized basis are preferred [43], The approach has recently been extended to also include matrix elements of a spin-orbit Hamiltonian. A number of RASSCF wave functions are used as a basis set to construct the spin-orbit Hamiltonian, which is then diagonalized [19, 44],... 

The least ambiguous and most appropriate description of the atom after the collision is in terms of the density matrix (Blum, 1981), whose elements are bilinear combinations of scattering amplitudes for different magnetic substates. For the sake of simplicity we restrict ourselves to the most common case, in which the target is initially in an S state and the excitation involves the transfer of one electron from an s orbital to a p orbital in the independent-particle approximation. In atoms with one active electron the transition is — P. If there are two active electrons it is — P. We use the LS-coupling scheme. 

In principle, using the above formalism the current density and the transfer matrix element can be evaluated at any level of the electronic structure calculations. Here we consider the Hartree-Fock calculations. 

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