Dipole expansion

Nonlinear processes being basically of Intramolecular nature, corresponding terms In the macroscopic and microscopic dipoles expansions can be related by the following tensorlal summation (given here for SHG coefficients), following an oriented gas description ... 

A simple model, known as the Internal equivalent field model (9) (see "Figure 1") accounts for the different p values of mono-substltuted benzene derivatives R-X, and relates them to the respective donor or acceptor strength of X. It Is assumed In this model that the substituent action on the it electrons of the ring Is equivalent to that of a D-C field EQ with direction and Intensity related to the substituent electronegativity. Identifying dipole expansions of R-X In presence of E and of R In presence of E0 + E yields ... 

An alternative formulation examines the molecular energy expansion, rather than the previous dipole expansion, with respect to the field ... 

Fig. 47. Convergency properties of the multipole expansion of electrostatic energy. 1F(R) is the mean value of electrostatic potential on a sphere of radius R calculated by a) dipole expansion terms only, b) dipole and quadrupole, c) dipole, quadrupole and octopole terms, d) as c) plus hexadecapole terms e) SCF values. The left side of figure refers to ammonia, the right one to aziridine...

In the dipole expansion the same results holds also for V... 

These moments are related to many physical properties. The Thomas-Kulm-Reiche sum rule says that. S (0) equals the number of electrons in the molecule. Other sum rules [36] relate S(2),, S (1) and. S (-l) to ground state expectation values. The mean static dipole polarizability is md = e-S(-2)/m,.J Q Cauchy expansion... 

The expansion of the perturbation w(r 2> tenns of inultipole potentials (e.g. dipole-dipole, dipole-... 

For many molecules the reduced dipole moment p = (p /( a )) is greater than 1 and the tenns in the successive tenns in the X expansion oscillate widely. Stell, Rasaiah and Narang [M] suggested taming this by replacing the tnincated expansion by the Fade approximant... 

The molecular dipole moment (not the transition dipole moment) is given as a Taylor series expansion about the equilibrium position... 

Raman scattering has been discussed by many authors. As in the case of IR vibrational spectroscopy, the interaction is between the electromagnetic field and a dipole moment, however in this case the dipole moment is induced by the field itself The induced dipole is pj j = a E, where a is the polarizability. It can be expressed in a Taylor series expansion in coordinate isplacement... 

Since the electric field is a polar vector, it acts to break the inversion synnnetry and gives rise to dipole-allowed sources of nonlinear polarization in the bulk of a centrosymmetric medium. Assuming that tire DC field, is sufficiently weak to be treated in a leading-order perturbation expansion, the response may be written as... 

The three moments higher than the quadrupole are the octopole, hexapole and decapoli. Methane is an example of a molecule whose lowest non-zero multipole moment is the octopole. The entire set of electric moments is required to completely and exactly describe the distribution of charge in a molecule. However, the series expansion is often truncated after the dipole or quadrupole as these are often the most significant. 

Irude model only considers the dipole-dipole interaction if higher-order terms, due to e-quadrupole, quadrupole-quadrupole, etc., interactions are included as well as other i in the binomial expansion, then the energy of the Drude model is more properly an as a series expansion ... 

The multipole moments (charge, dipole, quadrupole) of each cell are then calculated mining over the atoms contained within the cell. The interaction between all of the 3 in the cell and another atom outside the cell (or indeed another cell) can then be lated using an appropriate multipole expansion (see Section 4.9.1). 

The first term in this expansion, when substituted into the integral over the vibrational eoordinates, gives ifj(Re) , whieh has the form of the eleetronie transition dipole multiplied by the "overlap integral" between the initial and final vibrational wavefunetions. The if i(Rg) faetor was diseussed above it is the eleetronie El transition integral evaluated at the equilibrium geometry of the absorbing state. Symmetry ean often be used to determine whether this integral vanishes, as a result of whieh the El transition will be "forbidden". 

The second term in the above expansion of the transition dipole matrix element Za 3 if i/3Ra (Ra - Ra,e) can become important to analyze when the first term ifi(Re) vanishes (e.g., for reasons of symmetry). This dipole derivative term, when substituted into the integral over vibrational coordinates gives... 

The molecular quantities can be best understood as a Taylor series expansion. For example, the energy of the molecule E would be the sum of the energy without an electric field present, Eq, and corrections for the dipole, polarizability, hyperpolarizability, and the like ... 

The multipole expansion gives exactly that expression. If the charge distribution shown has an overall charge Q, an electric dipole pe, an electric quadrupole 0g, and so on, then we write... 

The change in the dipole moment with respect to a geometry displacement along a normal coordinate is approximately proportional to the intensity of an IR absorption. In the so-called double harmonic approximation (terminating the expansion at first order in the electric field and geometry), the intensity is (except for some constants)... 

The charge distribution of the molecule can be represented either as atom centred charges or as a multipole expansion. For a neutral molecule, the lowest-order approximation considers only the dipole moment. This may be quite a poor approximation, and fails completely for symmetric molecules which do not have a dipole moment. For obtaining converged results it is often necessarily to extend the expansion up to order 6 or more, i.e. including dipole, quadrupole, octupole, etc. moments. 

The spherical cavity, dipole only, SCRF model is known as the OnMger model.The Kirkwood model s refers to a general multipole expansion, if the cavity is ellipsoidal the Kirkwood—Westheimer model arise." A fixed dipole moment of yr in the Onsager model gives rise to an energy stabilization. 

In connection with electronic strucmre metlrods (i.e. a quantal description of M), the term SCRF is quite generic, and it does not by itself indicate a specific model. Typically, however, the term is used for models where the cavity is either spherical or ellipsoidal, the charge distribution is represented as a multipole expansion, often terminated at quite low orders (for example only including the charge and dipole terms), and the cavity/ dispersion contributions are neglected. Such a treatment can only be used for a qualitative estimate of the solvent effect, although relative values may be reasonably accurate if the molecules are fairly polar (dominance of the dipole electrostatic term) and sufficiently similar in size and shape (cancellation of the cavity/dispersion terms). 

The key element in London s approach is the expansion of the electrical potential energy in multipole series. Since neutral molecules or portions of molecules are involved, the leading term is that for dipole-dipole interaction. While attention has been given to higher-order terms, these are usually small, and the greater need seems to be for improved treatment of the dipole-dipole terms. London used second order perturbation theory in his treatment, but Slater and Kirkwood38,21 soon followed with a variation method treatment which yielded similar results. Other individual papers will be mentioned later, but the excellent review of Mar-genau26 should not be overlooked. 

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