Higher multipoles

The multipole moment of rank n is sometimes called the 2"-pole moment. The first non-zero multipole moment of a molecule is origin independent but the higher-order ones depend on the choice of origin. Quadnipole moments are difficult to measure and experimental data are scarce [17, 18 and 19]. The octopole and hexadecapole moments have been measured only for a few highly syimnetric molecules whose lower multipole moments vanish. Ab initio calculations are probably the most reliable way to obtain quadnipole and higher multipole moments [20, 21 and 22]. 

There are higher multipole polarizabilities tiiat describe higher-order multipole moments induced by non-imifonn fields. For example, the quadnipole polarizability is a fourth-rank tensor C that characterizes the lowest-order quadnipole moment induced by an applied field gradient. There are also mixed polarizabilities such as the third-rank dipole-quadnipole polarizability tensor A that describes the lowest-order response of the dipole moment to a field gradient and of the quadnipole moment to a dipolar field. All polarizabilities of order higher tlian dipole depend on the choice of origin. Experimental values are basically restricted to the dipole polarizability and hyperpolarizability [21, 24 and 21]. Ab initio calculations are an imponant source of both dipole and higher polarizabilities [20] some recent examples include [26, 22] ... 

Soholes G D and Andrews D L 1997 Damping and higher multipole effeots in the quantum eleotrodynamioal model for eleotronio energy transfer in the oondensed phase J. Chem. Phys. 107 5374-84... 

Molecular dipole moments are often used as descriptors in QPSR models. They are calculated reliably by most quantum mechanical techniques, not least because they are part of the parameterization data for semi-empirical MO techniques. Higher multipole moments are especially easily available from semi-empirical calculations using the natural atomic orbital-point charge (NAO-PC) technique [40], but can also be calculated rehably using ab-initio or DFT methods. They have been used for some QSPR models. 

Gaussian also predicts dipole moments and higher multipole moments (through hexadecapole). The dipole moment is the first derivative of the energy with respect to an applied electric field. It is a measure of the asymmetry in the molecular charge distribution, and is given as a vector in three dimensions. For Hartree-Fock calculations, this is equivalent to the expectation value of X, Y, and Z, which are the quantities reported in the output. 

The first term in (4) is the band energy contribution, as given by the GPM. The second term represents electrostatic interactions of higher multipoles and is usually neglibly small. 

Another problem arises from the presence of higher terms in the multipole expansion of the electrostatic interaction. While theoretical formulas exist for these also, they are even more approximate than those for the dipole-dipole term. Also, there is the uncertainty about the exact form of the repulsive interaction. Quite arbitrarily we shall group the higher multipole terms with the true repulsive interaction and assume that the empirical repulsive term accounts for both. The principal merit of this assumption is simplicity the theoretical and experimental coefficients of the R Q term are compared without adjustment. Since the higher multipole terms are known to be attractive and have been estimated to amount to about 20 per cent of the total attractive potential at the minimum, a rough correction for their possible effect can be made if it is believed that this is a preferable assumption. 

Electron population parameters of inner monopoles were constrained to be equal for all 40 non-H atoms. Single exponentials r exp(-ar) were adopted as radial functions for the higher multipoles, with n = 2, 2, 3 respectively for dipole, quadrupole, and octopole of the species C, N and 0, and n = 4, 4, 4 for the same multipoles of the S atom. A radial scaling parameter k, to shape the outer shell monopoles, and the exponential parameter a of all non-H atomic species were also refined. H atoms were initially given scattering factors taken from the H2 molecule [15] and polarised in the direction of the atom to which they are bonded. 

The dislocations in a tangle can lower their potential energy by aligning themselves to form dipoles and higher multipoles. The stress needed to push subsequent dislocations through a tangle (dipoles and multipoles) is proportional to the elastic shear modulus so it may be expected that the hardnesses of simple metals are proportional to their shear moduli. Figure 2.7 confirms this. 

Of course, the na, o a 11, and oah NBOs of the H-bonding region are important contributors to the dipole, quadrupole, and higher-multipole moments of the monomers. Thus, certain multipoles may appear to explain the geometry through their close connections to these NBOs, but this is not an incisive way to describe the physical situation. 

Here p is the stellar dipole magnetic moment and M is the mass accretion rate through the disk. For this formula we assume a purely dipolar field higher multipoles weaken the dependence on M because the field is effectively stiffen... 

The dipole approximation is valid only for point dipoles, i.e. when the donor-acceptor separation is much larger than the molecular dimensions. At short distances or when the dipole moments are large, it should be replaced by a monopole-monopole expansion. Higher multipole terms should also be included in the calculations. 

All the above methods are somehow based on an orbital hypothesis. In fact, in the multipolar model, the core is typically frozen to the isolated atom orbital expansion, taken from Roothan Hartree Fock calculations (or similar [80]). Although the higher multipoles are not constrained to an orbital model, the radial functions are typically taken from best single C exponents used to describe the valence orbitals of a given atom [81]. Even tighter is the link to the orbital approach in XRCW, XAO, or VOM as described above. Obviously, an orbital assumption is not at all mandatory and other methods have been developed, for example those based on the Maximum Entropy Method (MEM) [82-86] where the constraints/ restraints come from statistical considerations. 

As stated in an earlier paragraph, the sharp emission and absorption lines observed in the trivalent rare earths correspond to/->/transitions, that is, between free ion states of the same parity. Since the electric-dipole operator has odd parity,/->/matrix elements of it are identically zero in the free ion. On the other hand, however, because the magnetic-dipole operator has even parity, its matrix elements may connect states of the same parity. It is also easily shown that electric quadrupole, and other higher multipole transitions are possible. 

Representation of the density n(r) [or, effectively, the electrostatic potential — 0(r)] near any one of the sinks as an expansion in the monopole and dipole contribution only [as in eqn. (230c)] is generally, unsatisfactory. This is precisely the region where the higher multipole moments make their greatest contribution. However, the situation can be improved considerably. Felderhof and Deutch [25] suggested that the physical size of the sinks and dipoles be reduced from R to effectively zero, but that the magnitude of all the monopoles and dipoles, p/, are maintained, by the definition... 

With this notation, the electric charge qo of a monopole equals Qoo-Cartesian dipole components px, py, pz, are related to the spherical tensor components as Ql0 = pz, Qi i = +(px ipy)/y/2, with i designating the imaginary unit. Similar relationships between Cartesian and spherical tensor components can be specified for the higher multipole moments (Gray and Gubbins 1984). 

Higher multipole moments have rarely been used but expressions of the various dipole components can be obtained in the same way. 

Although 1 is one of the best investigated molecules, there is, apart from data concerning its electron density distribution, very little information available on its one-electron properties. In principle, accurate data could be obtained by correlation-corrected ab initio methods, but almost nothing has been done in this direction, which of course has to do with the fact that experimental data on one-electron properties of 1 are also rare, and therefore, it is difficult to assess the accuracy and usefulness of calculated one-electron properties such as higher multipole moments, electric field gradients, etc. 

The Born equation is based on the simple model of a spherical ion with a single charge at its centre. Such an ion has no dipole moment and no higher multipole moments, but real molecular ions are of course much more complex. Since the electrical charge is distributed among all the atoms of the... 

The discussion above is focused on dipole-dipole collision processes, but it may easily be extended to higher multipole processes. If atoms 1 and 2 have 2k pole moments of n2k and n2W respectively, when the atoms are separated by a distance r the interaction V due to these multipoles is... 

For q and n the definitions are unambiguous. For higher multipoles it is often convenient to define the quantities in different ways the quadrupole moment is often defined as... 

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