Quantum mechanical formulation

The Poisson equation has been used for both molecular mechanics and quantum mechanical descriptions of solvation. It can be solved directly using numerical differential equation methods, such as the finite element or finite difference methods, but these calculations can be CPU-intensive. A more efficient quantum mechanical formulation is referred to as a self-consistent reaction field calculation (SCRF) as described below. 

Dirac equation one-electron relativistic quantum mechanics formulation direct integral evaluation algorithm that recomputes integrals when needed distance geometry an optimization algorithm in which some distances are held fixed... 

HyperChem quantum mechanical calculations are ab initio and semi-empirical. Ab initio calculations use parameters (contracted basis functions) associated with shells, such as an s shell, sp shell, etc., or atomic numbers (atoms). Semi-empirical calculations use parameters associated with specific atomic numbers. The concept of atom types is not used in the conventional quantum mechanics methods. Semi-empirical quantum mechanics methods use a rigorous quantum mechanical formulation combined with the use of empirical parameters obtained from comparison with experiment. If parameters are available for the atoms of a given molecule, the ab initio and semi-empirical calculations have an a priori aspect when compared with a molecular mechanics calculation, letting... 

It is now known that the view of electrons in individual well-defined quantum states represents an approximation. The new quantum mechanics formulated in 1926 shows unambiguously that this model is strictly incorrect. The field of chemistry continues to adhere to the model, however. Pauli s scheme and the view that each electron is in a stationary state are the basis of the current approach to chemistry teaching and the electronic account of the periodic table. The fact that Pauli unwittingly contributed to the retention of the orbital model, albeit in modified form, is somewhat paradoxical in view of his frequent criticism of the older Bohr orbits model. For example Pauli writes,... 

It is a characteristic feature of all these relativistic equations that in addition to positive energy solutions, they admit of negative energy solutions. The clarification of the problems connected with the interpretation of these negative energy solutions led to the realization that in the presence of interaction, a one particle interpretation of these equations is difficult and that in a consistent quantum mechanical formulation of the dynamics of relativistic systems it is convenient to deal from the start with an indefinite number of particles. In technical language this is the statement that one is to deal with quantized fields. 

In the quantum mechanical formulation of electron transfer (Atkins, 1984 Closs et al, 1986) as a radiationless transition, the rate of ET is described as the product of the electronic coupling term J2 and the Frank-Condon factor FC, which is weighted with the Boltzmann population of the vibrational energy levels. But Marcus and Sutin (1985) have pointed out that, in the high-temperature limit, this treatment yields the semiclassical expression (9). 

In the classical approach, it is relatively simple to calculate the solvation energies. However, in the quantum mechanical formulations, the electronic structure of the solute molecule depends on the reaction held and the reaction held in turn depends on the structure of the solute. It is a typical nonlinear problem and has to be solved iteratively. Several approaches have been proposed for solving this problem [8-11]. All of them are based on the modihcation of the Hamiltonian in the following equation ... 

The aforementioned applications of recursive methods in reaction dynamics do not involve diagonalization explicitly. In some quantum mechanical formulations of reactive scattering problems, however, diagonalization of sub-Hamiltonian matrices is needed. Recursive diagonalizers for Hermitian and real-symmetric matrices described earlier in this chapter have been used by several authors.73,81... 

Marcus developed a quantum mechanical formulation of Kassel-Rice-Ramsperger theories in which zero point energies have been taken into account (see flow chart). However, due to lack of data for individual molecules it is difficult to apply the theory of Rice-Ramsperger-Kassel-Marcus (RRKM)... 

Second, the mapping approach to nonadiabatic quantum dynamics is reviewed in Sections VI-VII. Based on an exact quantum-mechanical formulation, this approach allows us in several aspects to go beyond the scope of standard mixed quantum-classical methods. In particular, we study the classical phase space of a nonadiabatic system (including the discussion of vibronic periodic orbits) and the semiclassical description of nonadiabatic quantum mechanics via initial-value representations of the semiclassical propagator. The semiclassical spin-coherent state method and its close relation to the mapping approach is discussed in Section IX. Section X summarizes our results and concludes with some general remarks. 

The similar appearance of the quantum and classical Liouville equations has motivated several workers to construct a mixed quantum-classical Liouville (QCL) description [27 4]. Hereby a partial classical limit is performed for the heavy-particle dynamics, while a quantum-mechanical formulation is retained for the light particles. The quantities p(f) and H in the mixed QC formulation are then operators with respect to the electronic degrees of freedom, described by some basis states 4> ), and classical functions with respect to the nuclear degrees of freedom with coordinates x = x, and momenta p = pj — for example. 

A QUANTUM MECHANICAL FORMULATION OF THE ELECTROCHEMICAL CURRENT DENSITY... 

These contributions were taken explicitly to a quantum mechanical level by Levich during the 1960s and then by Schmickler, who finally published an elegant summary of quantum electrode kinetics in 1996. Schmickler stressed the quantum mechanical formulation made by Levich, Dogonadze, and Kuznetsov. However, his summary of the quantum mechanical formulation of electrode reactions still possesses the Achilles heel of earlier formulations it is restricted to nonbond-breaking, seldom-occurring outer-sphere reactions and involves the harmonic approximation for the energy variation, which is the main reason of such theories cannot replicate Tafel s law (Khan and Sidik, 1997). 

In terms of spectroscopic observables, the potential energy function is that function V(r) which, when inserted into the quantum mechanical formulation of the vibration problem, gives the observed vibrational levels. In beam experiments, it is the potential which gives the observed scattering. In chemical excitation processes, it is the surface which predicts the observed total cross section and the observed distribution of products over internal energy states. Potential energy functions may be calculated from first principles14, or they may be constructed... 

Quantum-Mechanical Formulation of the Franck-Condon Principle... 

Franck-Condon integral, 97,132 Franck-Condon principle, 68, 94, 169 quantum mechanical formulation of, 96... 

The last fundamental aspect characterizing PCM methods, i.e. their quantum mechanical formulation, is presented by Cammi for molecular systems in their ground electronic states and by Mennucci for electronically excited states. In both contributions, particular attention is devoted to the specific aspect characterizing PCM (and similar) approaches, namely the necessity to introduce an effective nonlinear Hamiltonian which describes the solute under the effect of the interactions with its environment and determines how these interactions affect the solute electronic wavefunction and properties. 

The Hamilton-Jacobi form of the classical equations of motion has been shown to have provided the basis for the quantum-mechanical formulations according to Sommerfeld, Heisenberg, Schrodinger and Bohm. Each of these formulations inspired its own peculiar interpretation of quantum effects, despite their common basis. Each of the different points of view still has its adherents and the debates about their relative merits continue. Closer scrutiny shows that the Sommerfeld and Heisenberg systems assume quanta to be particles in the classical sense, although Heisenberg considered electronic positions to be fundamentally unobservable. 

The quantum-mechanical formulation of the progress of a reaction such as... 

After the choice of the relevant Lewis structures has been made, the following step involves their quantum mechanical formulation. Each Lewis structure corresponds to a set of atomic orbitals which are singly or doubly occupied, as illustrated in 9-11 for the F2 molecule. 

This simple picture has to be abandoned once rigorous quantum-mechanical formulation is sought. Within such a formulation, x >s given by the statistical average [25],... 

The quantum mechanical formulation of this principle is that the intensity of a vihronic transition is proportional to the square of the overlap integral between the vibrational wavefunctions of the two states that are involved in the transition. 

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