Molecular electronic Hamiltonian

Several categories of models appear as the basis for the study of molecular electronics in general, and molecular transport junctions in particular. These are the geometrical (or molecular), Hamiltonian, and transport analysis models. 

Keywords Intramolecular kirchhoff laws Molecular electronics Molecular logic gates Single molecule electronic circuits Quantum hamiltonian computing... 

Before investigating the qualitative concepts of the VSEPR model it is worth noting that the details of the interactions between the electron pairs have been ascribed to a size-Pauli exclusion principle result . But objects do not repel each other simply because of their sizes (i.e. interpenetrations) only if the constituents of the objects interact is any interaction possible10). If we are to use the idea of orbital size at all we must avoid the danger of contrasting a phenomenon (electron repulsion) with one of its manifestations (steric effects). The only quantitative tests which we can apply to the VSEPR model are ones based on the terms in the molecular Hamiltonian specifically, electron repulsion. 

The Hamiltonians of interest in molecular electronic structure theory correspond to the choices... 

An ab initio calculation uses the correct molecular electronic Hamiltonian (1.275) and does not introduce experimental data (other than the values of the fundamental physical constants) into the calculation. A semiempirical calculation uses a Hamiltonian simpler than the correct one, and takes some of the integrals as parameters whose values are determined using experimental data. The Hartree-Fock SCF MO method seeks the orbital wave function 0 that minimizes the variational integral <(4> //el initio method. Semiempirical methods were developed because of the difficulties involved in ab initio calculation of medium-sized and large molecules. We can... 

Thus suppose we had included the interaction of the radiation s magnetic field B with the atomic or molecular electrons and nuclei. The Hamiltonian for this interaction is [Equation (1.268)] -B , where p is the magnetic dipole-moment operator for the system. This gives additional terms in cm that are proportional to... 

We add the operator —p, ER to the total molecular Hamiltonian. According to Eq. (3.1), the electronic Hamiltonian of the molecule in the field due to the solvent is then He — p ER. The electronic Schrodinger equation is then solved using this modified Hamiltonian. This leads to a self-consistent solution where the electronic wave function and the electronic energy are modified due to the solvent field. Thus, polarization of the molecular electronic density (as described approximately above) is automatically included in this approach. 

The main purpose of DFT is to simplify evaluation of the final term in the molecular electronic hamiltonian ... 

We will mostly use second quantization and thereby represent the molecular electronic Hamiltonian in Eq. (13-2) as... 

The method discussed here for the inclusion of relativistic effects in molecular electronic structure calculations is grounded in the Dirac-Fock approximation for atomic wave functions (29). The premise is that the major relativistic effects of the Dirac Hamiltonian are manifested in the core region, involving the core electrons, and that these effects propagate to the valence electrons. In addition, there are direct relativistic effects on valence electrons penetrating into the core region. Insofar as this is true, the valence electrons can be treated using a nonrelativistic Hamiltonian to which is added an operator, the relativistic effective core potential (REP). The REP formally, incorporates relativistic effects due to core electrons and to interactions of valence electrons with core electrons in an internally consistent way. 

The model that is outlined above is generated from a one-electron Hamiltonian and is only an approximation to the tme wavefimction for a multielectron system. As suggested earlier, other components may be added as a linear combination to the wavefimction that has just been derived. There are many techniques used to alter the original trial wavefimction. One of these is frequently used to improve wavefimctions for many types of quantum mechanical systems. Typically a small amount of an excited-state wavefimction is included with the minimal basis trial fimction. This process is called configuration interaction (Cl) because the new trial function is a combination of two molecular electron configurations. For example, in the H2+ system a new trial fimction can take the form... 

This contains an TCP of the TpaL tensor, which is derived from the electron spin and dipole-dipole interaction tensor(See equation (11)). Hence, the first question we confront is whether those tensors are correlated or not. In case they are not the total TCP can be decomposed into a product of auto correlations for the the electron spin and dipole-dipole interaction tensor, respectively. In case they are, however, it is necessary to consider the whole TCP and the electron spin has to be correlated with the dipole-dipole interaction tensor. The time dependence in the electron spin tensor can be obtained by integrating the time dependent Schrbdinger equation for the electron spin under the electron spin Hamiltonian. The electron spin is just like the nuclear spin precessing around the external magnetic field and influenced by molecular dynamics. 

A direct consequence of the observation that Eqs. (12.55) provide also golden-rule expressions for transition rates between molecular electronic states in the shifted parallel harmonic potential surfaces model, is that the same theory can be applied to the calculation of optical absorption spectra. The electronic absorption lineshape expresses the photon-frequency dependent transition rate from the molecular ground state dressed by a photon, g) = g, hco ), to an electronically excited state without a photon, x). This absorption is broadened by electronic-vibrational coupling, and the resulting spectrum is sometimes referred to as the Franck-Condon envelope of the absorption lineshape. To see how this spectrum is obtained from the present formalism we start from the Hamiltonian (12.7) in which states L and R are replaced by g) and x) and Vlr becomes Pgx—the coupling between molecule and radiation field. The modes a represent intramolecular as well as intermolecular vibrational motions that couple to the electronic transition... 

In classical mechanics, positions and momenta are treated on an equal footing in the Hamiltonian picture. In quantum mechanics, they become operators, but it is true that the position r and momentum p of a particle are appropriate conjugate variables that can entirely equivalently describe a state of a system under the commutation relation [r, p] = i (Dirac, 1958). This equivalence is usually demonstrated by the example of the onedimensional harmonic oscillator. The choice of the most appropriate representation depends on convenient description of the phenomenon considered. Generally, the position representation is useful for most bound-state problems such as atomic and molecular electronic structures as well as for many scattering problems. The momentum-space treatment... 

Nieuwpoort, W. C., Aerts, P. J. C. and Visscher, L. (1994) Molecular electronic structure calculations based on the Dirac-Coulomb-(Breit) Hamiltonian. In Malli (1994), pp. 59-70. 

It is well known that, in view of the sheer mathematical complexity that we face when we try to solve Schrodinger s equation for the simplest molecular systems (already for the one-electron H cation [9]), we have to focus on the design of computationally manageable, yet reliable, approximation schemes, based on various model Hamiltonians. Even when ignoring the relahvistic elfects and freezing the nuclear motion via the Bom-Oppenheimer approximation [10], the problem is still too formidable for any system having more than two electrons. For this very reason, almost all quantum-mechanical treatments of the molecular electronic structure are based on hnite dimensional models. 

Debashis Mukherjee is a Professor of Physical Chemistry and the Director of the Indian Association for the Cultivation of Science, Calcutta, India. He has been one of the earliest developers of a class of multi-reference coupled cluster theories and also of the coupled cluster based linear response theory. Other contributions by him are in the resolution of the size-extensivity problem for multi-reference theories using an incomplete model space and in the size-extensive intermediate Hamiltonian formalism. His research interests focus on the development and applications of non-relativistic and relativistic theories of many-body molecular electronic structure and theoretical spectroscopy, quantum many-body dynamics and statistical held theory of many-body systems. He is a member of the International Academy of the Quantum Molecular Science, a Fellow of the Third World Academy of Science, the Indian National Science Academy and the Indian Academy of Sciences. He is the recipient of the Shantiswarup Bhatnagar Prize of the Council of Scientihc and Industrial Research of the Government of India. 

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