Electron-nuclear separations

In principle, it is well to separate the external constants of the motion (see Section IV-A) before electronic-nuclear separation, as the remaining motion will then correspond more readily with observables. Jepsen and Hirschfelder find, for example, that electronic-nuclear coupling is decreased if translation is removed prior to the Bom-Oppenheimer separation. The same can probably be said for rotational motion, but the difference would be more difficult to compute. 

The atomic reduced mass // is related to the nuclear mass Wjv and electron mass Me by /i=mgm /(mg+mjv), operates on the electronic coordinates, and r is the electron-nuclear separation. The eigenfunctions 6, )> and eigenvalues... 

Figure A93 The Coulomb potential V and radial force F, as a function of the electron-nuclear separation r.

Here the Z/ are the nuclear charges, r/ the electron-nuclear separations, ri2 the electron-electron separation and Ru the intemuclear separations. The summations are over all nuclei. The scalar term (1.4.42) represents the nuclear-repulsion eneigy - it is simply added to the Hamiltonian and makes the same contribution to matrix elements as in first quantization since the inner product of two ON vectors is identical to the overlap of the determinants. The molecular one- and two-electron integrals (1.4.40) and (1.4.41) may be calculated using the techniques described in Chapter 9. 

There can be subtle but important non-adiabatic effects [14, ll], due to the non-exactness of the separability of the nuclei and electrons. These are treated elsewhere in this Encyclopedia.) The potential fiinction V(R) is detennined by repeatedly solving the quantum mechanical electronic problem at different values of R. Physically, the variation of V(R) is due to the fact that the electronic cloud adjusts to different values of the intemuclear separation in a subtle interplay of mutual particle attractions and repulsions electron-electron repulsions, nuclear-nuclear repulsions and electron-nuclear attractions. 

DFT methods compute electron correlation via general functionals of the electron density (see Appendix A for details). DFT functionals partition the electronic energy into several components which are computed separately the kinetic energy, the electron-nuclear interaction, the Coulomb repulsion, and an exchange-correlation term accounting for the remainder of the electron-electron interaction (which is itself... 

When multi-electron atoms are combined to form a chemical bond they do not utilize all of their electrons. In general, one can separate the electrons of a given atom into inner-shell core electrons and the valence electrons which are available for chemical bonding. For example, the carbon atom has six electrons, two occupy the inner Is orbital, while the remaining four occupy the 2s and three 2p orbitals. These four can participate in the formation of chemical bonds. It is common practice in semi-empirical quantum mechanics to consider only the outer valence electrons and orbitals in the calculations and to replace the inner electrons + nuclear core with a screened nuclear charge. Thus, for carbon, we would only consider the 2s and 2p orbitals and the four electrons that occupy them and the +6 nuclear charge would be replaced with a +4 screened nuclear charge. 

The origin of postulate (iii) lies in the electron-nuclear hyperfine interaction. If the energy separation between the T and S states of the radical pair is of the same order of magnitude as then the hyperfine interaction can represent a driving force for T-S mixing and this depends on the nuclear spin state. Only a relatively small preference for one spin-state compared with the other is necessary in the T-S mixing process in order to overcome the Boltzmann polarization (1 in 10 ). The effect is to make n.m.r. spectroscopy a much more sensitive technique in systems displaying CIDNP than in systems where only Boltzmann distributions of nuclear spin states obtain. More detailed consideration of postulate (iii) is deferred until Section II,D. 

Molecular mechanics force fields rest on four fundamental principles. The first principle is derived from the Bom-Oppenheimer approximation. Electrons have much lower mass than nuclei and move at much greater velocity. The velocity is sufficiently different that the nuclei can be considered stationary on a relative scale. In effect, the electronic and nuclear motions are uncoupled, and they can be treated separately. Unlike quantum mechanics, which is involved in determining the probability of electron distribution, molecular mechanics focuses instead on the location of the nuclei. Based on both theory and experiment, a set of equations are used to account for the electronic-nuclear attraction, nuclear-nuclear repulsion, and covalent bonding. Electrons are not directly taken into account, but they are considered indirectly or implicitly through the use of potential energy equations. This approach creates a mathematical model of molecular structures which is intuitively clear and readily available for fast computations. The set of equations and constants is defined as the force... 

Hence, one should expect that, along the ESP at sufficiently large inter-nuclear separation, the solvent will overcome the delocalizing effects of the electronic resonance coupling, and localize the solute charge distribution... 

Finally, a possible use of these coupling constants as reactivity indices has been commented upon in both the one- and two-reactant approaches. In the interreactant decoupled applications the molecular compliants, obtained from calculations on separate reactants, can be used directly to qualitatively predict the intrareactant effects resulting from the interreactant CT. The building blocks of the combined electronic-nuclear Hessian for the two-reactant system have been discussed. The corresponding blocks of the generalized compliance matrix have also been identified. In such a complete, two-reactant treatment of reactants in the combined system, the additional calculations on the reactive system as a whole would be required. 

Figure 21.3 Diagrammatic representation of Potential Energy of a diatomic molecule showing (A) Potential Energy-Nuclear Separation Curves (B) Relationship between Electronic Transitions and Absorption Curves.

An interesting recent development is the application of an electron-nuclear-dynamics code [68] to penetration phenomena [69]. The scheme is capable of treating multi-electron systems and may he particularly useful for low-velocity stopping in insulating media, where alternative treatments are essentially unavailable. However, conceptional problems in the data analysis need attention, such as separation of nuclear from electronic stopping and, in particular, the very definition of stopping force as discussed in Section 5.2. 

The SnI activation free energies and transition-state stractnre for the series t-bntyl chloride, -bromide, and -iodide in several solvents over a wide polarity range have been examined theoretically. The analysis is accomplished by nsing a two-state valence bond representation for the solute electronic stractnre, in combination with a two-dimensional free energy formalism in terms of the alkyl halide nuclear separation... 

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