Hamiltonian, electromagnetic

The Hamiltonian considered above, which connmites with E, involves the electromagnetic forces between the nuclei and electrons. However, there is another force between particles, the weak interaction force, that is not invariant to inversion. The weak charged current mteraction force is responsible for the beta decay of nuclei, and the related weak neutral current interaction force has an effect in atomic and molecular systems. If we include this force between the nuclei and electrons in the molecular Hamiltonian (as we should because of electroweak unification) then the Hamiltonian will not conuuiite with , and states of opposite parity will be mixed. However, the effect of the weak neutral current interaction force is mcredibly small (and it is a very short range force), although its effect has been detected in extremely precise experiments on atoms (see, for... 

In addition, there could be a mechanical or electromagnetic interaction of a system with an external entity which may do work on an otherwise isolated system. Such a contact with a work source can be represented by the Hamiltonian U p, q, x) where x is the coordinate (for example, the position of a piston in a box containing a gas, or the magnetic moment if an external magnetic field is present, or the electric dipole moment in the presence of an external electric field) describing the interaction between the system and the external work source. Then the force, canonically conjugate to x, which the system exerts on the outside world is... 

Two states /a and /b that are eigenfunctions of a Hamiltonian Hq in the absence of some external perturbation (e.g., electromagnetic field or static electric field or potential due to surrounding ligands) can be "coupled" by the perturbation V only if the symmetries of V and of the two wavefunctions obey a so-called selection rule. In particular, only if the coupling integral (see Appendix D which deals with time independent perturbation theory)... 

This potential is referred to in electromagnetism texts as the retarded potential. It gives a clue as to why a complete relativistic treatment of the many-body problem has never been given. A theory due to Darwin and Breit suggests that the Hamiltonian can indeed be written as a sum of nuclear-nuclear repulsions, electron-nuclear attractions and electron-electron repulsions. But these terms are only the leading terms in an infinite expansion. 

Hie hamiltonian describing the negaton-positon field interacting with the electromagnetic field is... 

Navier-Stokes equations, 24 Negative criterion of Bendixon, 333 Negaton-positon field in an external field, 580 interacting with electromagnetic field, Hamiltonian for, 645 interaction with radiation field, 642 Negaton-positon system, 540 Negaton scattering by an external field, 613... 

In the Hamiltonian conventionally used for derivations of molecular magnetic properties, the applied fields are represented by electromagnetic vector and scalar potentials [1,20] and if desired, canonical transformations are invoked to change the magnetic gauge origin and/or to introduce electric and magnetic fields explicitly into the Hamiltonian, see e.g. refs. [1,20,21]. Here we take as our point of departure the multipolar Hamiltonian derived in ref. [22] without recourse to vector and scalar potentials. 

The Hamiltonian for a charged particle in an electromagnetic field can be obtained from Hamilton s principle and Lagrange s equations of motion (Section 3.3) ... 

The Hamiltonian of helium, in the center of mass frame and under the action of an electromagnetic field polarized along the x axis, with field amplitude F and frequency w, reads, in atomic units,... 

Now we can write down the total Hamiltonian including into consideration the strong ird, interaction and the Hamiltonian of the electromagnetic field. We take the density of the Hamiltonian the strong 7rd interaction in the zero range approach ... 

Physics and chemistry are carried out in laboratory frames using coordinate systems to set up experimental devices. Before discussing quantum mechanical processes let us recall the form of the total Hamiltonian for a set of particles having charges qa and masses ma interacting with an electromagnetic field A. This Hamiltonian is given by ... 

A chemical interconversion requiring an intermediate stationary Hamiltonian means that the direct passage from states of a Hamiltonian Hc(i) to quantum states related to Hc(j) has zero probability. The intermediate stationary Hamiltonian Hc(ij) has no ground electronic state. All its quantum states have a finite lifetime in presence of an electromagnetic field. These levels can be accessed from particular molecular species referred to as active precursor and successor complexes (APC and ASC). All these states are accessible since they all belong to the spectra of the total Hamiltonian, so that as soon as those quantum states in the active precursor (successor) complex that have a non zero electric transition moment matrix element with a quantum state of Hc(ij) these latter states will necessarily be populated. The rate at which they are populated is another problem (see below). 

The model fundamental to all analyses of vibrational motion requires that the atoms in the system oscillate with small amplitude about some defined set of equilibrium positions. The Hamiltonian describing this motion is customarily taken to be quadratic in the atomic displacements, hence in principle a set of normal modes can be found in terms of these normal modes both the kinetic energy and the potential energy of the system are diagonal. The interaction of the system with electromagnetic radiation, i.e. excitation of specific normal modes of vibration, is then governed by selection rules which depend on features of the microscopic symmetry. It is well known that this model can be worked out in detail for small molecules and for crystalline solids. In some very favorable simple cases the effects of anharmonicity can be accounted for, provided they are not too large. 

The idea behind this conclusion was obtained as follows. The non-relativistic Hamiltonian for a system under an external electromagnetic field is given by... 

With the exception of recent extensions to electroweak theory [1] chemistry deals exclusively with electromagnetic interactions. The starting point for a quantum theory to describe these interactions is the Lagrangian formalism since it allows the correct identification of conjugated momenta appearing in the Hamiltonian [2]. Full-fledged quantum electrodynamics (QED) is based on a Lagrangian of the form... 

External fields are introduced in the relativistic free-particle operator hy the minimal substitutions (17). One should at this point carefully note that the principle of minimal electromagnetic coupling requires the specification of particle charge. This becomes particularly important for the Dirac equation which describes not only the electron, but also its antiparticle, the positron. We are interested in electrons and therefore choose q = — 1 in atomic units which gives the Hamiltonian... 

A systematic development of relativistic molecular Hamiltonians and various non-relativistic approximations are presented. Our starting point is the Dirac one-fermion Hamiltonian in the presence of an external electromagnetic field. The problems associated with generalizing Dirac s one-fermion theory smoothly to more than one fermion are discussed. The description of many-fermion systems within the framework of quantum electrodynamics (QED) will lead to Hamiltonians which do not suffer from the problems associated with the direct extension of Dirac s one-fermion theory to many-fermion system. An exhaustive discussion of the recent QED developments in the relevant area is not presented, except for cursory remarks for completeness. The non-relativistic form (NRF) of the many-electron relativistic Hamiltonian is developed as the working Hamiltonian. It is used to extract operators for the observables, which represent the response of a molecule to an external electromagnetic radiation field. In this study, our focus is mainly on the operators which eventually were used to calculate the nuclear magnetic resonance (NMR) chemical shifts and indirect nuclear spin-spin coupling constants. 

So far our discussion is limited to a single fermion in the free field or in the presence of an electromagnetic radiation field. In the following section, we will generalize the discussion to relativistic many-fermion Hamiltonians. 

Generally, it is not required to retain all the terms in the resulting approximate Hamiltonian, except those operators which describe the actual physical processes involved in the problem. For example, in the absence of an external electromagnetic field, the non-relativistic energy calculations only requires... 

To summarize, a detailed discussion of relativistic and non-relativistic forms of molecular Hamiltonians is presented. Our starting point is the Dirac one-fermion Hamiltonian in the presence of an external electromagnetic radiation field. 

The interaction Hamiltonian contains the operator A, corresponding to the vector potential A of the electromagnetic field.2 Excluding magnetic scattering, the interaction Hamiltonian is given by... 

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