External Electromagnetic Fields and Molecular Properties

In this chapter, we shall now come back to the question how physical observables are associated with proper operator descriptions, which has already been addressed in section 4.3. All preceding chapters dealt with the proper construction of Hamiltonians for the calculation of energies and wave functions of many electron systems. Here, we shall now transfer this knowledge to the construction of relativistic expressions for first-principles calculations of molecular properties for many-electron systems. The basic guideline for this is the fact that all molecular properties can be expressed as total electronic energy derivatives. 

Relativistic Quantum Chemistry. Markus Reiher and Alexander Wolf 

In general, they can all be properly dealt with in the framework of perturbation (response) theory. According to the discussion in section 5.4, we may add external electromagnetic fields acting on individual electrons to the one-electron terms in the Hamiltonian of Eq. (8.66). Fields produced by other electrons, so that contributions to the one- and two-electron interaction operators in Eq. (8.66) arise, are not of this kind as they are considered to be internal and are properly accounted for in the Breit (section 8.1) or Breit-Pauli Hamiltonians (section 13.2). Although the extemal-field-free Breit-Pauli Hamiltonian comprises all internal interactions, such as spin-spin and spin-other-orbit terms, they may nevertheless also be considered as a perturbation in molecular property calculations. While our derivation of the Breit-Pauli Hamiltonian did not include additional external fields (such as the magnetic field applied in magnetic resonance spectroscopies), we now need to consider these fields as well. 

However, other non-electromagnetic effects also influence the electronic structure. Examples are isotope shifts or electro-weak interactions, that lead to parity nonconservation. The latter result from the motion of a nucleus (in an atom relative to the center of mass) and yield a dependence of energy levels on the nuclear mass (and on the finite size of the nucleus, as we have already discussed in chapters 6 and 9). The energy levels are thus shifted, while the electromagnetic perturbations result in a splitting of these levels. 

The capabilities of molecular property calculations depend not only on the proper relativistic Hamiltonians, but also crucially on the consideration of electron-correlation effects due to the use of the mean-field orbital model. 

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I 15 External Electromagnetic Fields and Molecular Properties the second-order even term [610]... 

We will in this section consider the mathematical structure for computational procedures when calculating molecular properties of a quantum mechanical subsystem coupled to a classical subsystem. Molecular properties of the quantum subsystem are obtained when considering the interactions between the externally applied time-dependent electromagnetic field and the molecular subsystem in contact with a structured environment such as an aerosol particle. Therefore, we need to study the time evolution of the expectation value of an operator A and we express that as... 

The continuous spectrum is also present, both in physical processes and in the quantum mechanical formalism, when an atomic (molecular) state is made to interact with an external electromagnetic field of appropriate frequency and strength. In conjunction with energy shifts, the normal processes involve ionization, or electron detachment, or molecular dissociation by absorption of one or more photons, or electron tunneling. Treated as stationary systems with time-independent atom - - field Hamiltonians, these problems are equivalent to the CESE scheme of a decaying state with a complex eigenvalue. For the treatment of the related MEPs, the implementation of the CESE approach has led to the state-specific, nonperturbative many-electron, many-photon (MEMP) theory [179-190] which was presented in Section 11. Its various applications include the ab initio calculation of properties from the interaction with electric and magnetic fields, of multiphoton above threshold ionization and detachment, of analysis of path interference in the ionization by di- and tri-chromatic ac-fields, of cross-sections for double electron photoionization and photodetachment, etc. 

Some of the terms included in the Breit-Pauli Hamiltonian also describe small interactions that can be probed experimentally by inducing suitable excitations in the electron or nuclear spin space, giving rise to important contributions to observable NMR and ESR parameters. In particular, for molecular properties for which there are interaction mechanisms involving the electron spin, also the spin-orbit interaction (O Eqs. 11.13 and O 11.14) becomes important The Breit-Pauli Hamiltonian in O Eqs. 11.5-11.22, however, only includes molecule-external field interactions through the presence of a scalar electrostatic potential 0 (and the associated electric field F) and the appearance of the magnetic vector potential in the mechanical momentum operator (O Eq. 11.23). In order to extract in more detail the interaction between the electronic structure of a molecule and an external electromagnetic field, we need to consider in more detail the form of the scalar and vector potentials. 

Most of the recent literature on molecular collisions in external fields [1-3, 9, 10, 15, 16, 18, 19, 21, 23, 25, 27-84, 92] is focused on collisions of molecules at low and ultralow temperatures. As mentioned in the introduction, it is at temperatures < 10 K that strong electromagnetic fields are expected to have a noticeable effect on the scattering properties of molecules. The coupled-channel calculations... 

This section considers the theoretical background for calculating the molecular properties of a quantum mechanical subsystem exposed to a structured environment and interacting with an externally applied electromagnetic field. The time evolution of the expectation value of any operator A is determined using Ehrenfest s equation ... 

For molecules situated in/at and interacting with a structured environment, it is important to determine molecular properties of the molecules when they are exposed to an external time-dependent electromagnetic field. Methods for doing... 

Many molecular crystals exhibit polymorphism, that is different crystal structures, or phases, for the same chemical composition. A phase is a homogeneous part of the sample with identical properties, separated by the others by phase boundaries. The different polymorphs exhibit different physical properties as a consequence of the different packing of the same molecules. The transformation between different polymorphs may be driven by an intensive parameters such as temperature, hydrostatic pressure or also by external stimulating fields (electromagnetic field, light, etc.), and it is not... 

A large class of molecular properties arise from the interaction of molecules with electromagnetic fields. As emphasized previously, the external fields are treated as perturbations and so one considers only the effect of the fields on the molecule and not the effect of the molecule on the field. The electromagnetic fields introduced into the electronic wave equation is accordingly those of free space. From (79) one observes that in the absence of sources the electric field has zero divergence, and so both the electric and magnetic fields are purely transversal. It follows that the scalar potential is a constant and can be set to zero. In Coulomb gauge the vector potential is found from the equation... 

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