Multipole moments components

Advances in ab initio quantum mechanical calculations are providing ever more accurate molecular wavefunctions. The accuracy of a wavefunction is often tested by comparing the calculated dipole moment components (or multipole moment components) with observed values. There seem to be no easy shortcuts to obtaining high quality wavefunctions an elaborate set of basis functions and a lot of computer power are required. Fortunately, the rapid strides in computer power are making possible the calculation of many high quality wave-... 

It is apparent that the 7 take the place in this formulation of the interaction tensors T of the conventional Cartesian formulation, but it should be emphasized once again that all the formulae given here refer to multipole moment components in the local, molecule-fixed frame of each molecule, whereas the corresponding Cartesian formulae deal in space-fixed components throughout and require a separate transformation between molecule-fixed and space-fixed frames. ( Space-fixed is perhaps a misleading term here, since the calculation is commonly carried out in a coordinate system with one of its axes along the intermolecular vector. However, the point is that in the Cartesian tensor notation there has to be a common set of axes for the system as a whole, and this can be the molecule-fixed frame for at most one of the molecules involved.)... 

The long-range interactions between a pair of molecules are detemiined by electric multipole moments and polarizabilities of the individual molecules. MuJtipoJe moments are measures that describe the non-sphericity of the charge distribution of a molecule. The zeroth-order moment is the total charge of the molecule Q = Yfi- where q- is the charge of particle and the sum is over all electrons and nuclei in tlie molecule. The first-order moment is the dipole moment vector with Cartesian components given by... 

London-van der Waals forces, which are multipole interactions produced by correlation between fluctuating induced multipole moments in two nearly uncharged polar molecules. These forces also include dispersion forces that arise from the correlation between the movement of electrons in one molecule and those of neighboring molecules. The van der Waals dispersion interaction between two molecules is generally very weak, but when many groups of atoms in a polymeric structure act simultaneously, the van der Waals components are additive. 

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). 

For linear molecules, we choose the molecular axis to be along the z-axis of the molecular frame. In this case, Q/ = 0 for all n f 0 because the Y(m depend on cp as exp imcp. As a consequence, Q( becomes e-ma Q/o, which means that only Q/o = qe is invariant under rotation. In other words there is only one independent multipole moment for every order L Laboratory-fixed components thus become simply... 

Here a designates the trace of the polarizability tensor of one molecule (l/47i o) times the factor of a represents the electric fieldstrength of the quadrupole moment q2. Other non-vanishing multipole moments, for example, octopoles (e.g., of tetrahedral molecules), hexadecapoles (of linear molecules), etc., will similarly interact with the trace or anisotropy of the polarizability of the collisional partner and give rise to further multipole-induced dipole components. 

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

The potential outside the charge distribution and due to it is simply related to the moments, as is the interaction energy when an external field is applied.14 The multipole moments are thus very useful quantities and have been extensively applied in the theory of intermolecular forces, particularly at long range where the electrostatic contribution to the interaction may be expanded in moments. Their values are related to the symmetry of the system thus, for instance, a plane of symmetry indicates that the component of n perpendicular to it must be zero. Such multipoles are worth calculating in their own right. 

Three components (Q — —1,0,+1) of the multipole moment of rank K = 1 form the cyclic components of the vector. They are proportional to the mean value of the corresponding spherical functions (B.l) for angular momenta distribution in the state of the molecule as described by the probability density p 9,(p). These components of the multipole moments enable us to find the cyclic components of the angular momentum of the molecule ... 

The connection between the covariant cyclic and cartesian coordinates of the vector J yields Eq. (A.6), whilst (A.5) makes it possible to form the vector itself out of the components (J)q. As follows from (2.18), the components of the multipole moment pq characterize the preferred orientation of the angular momentum J in the molecular ensemble. Fig. 2.3(a, b) shows the probability density p(0, [Pg.30]

Five components (Q = —2,—1,0,1,2) of the multipole moment pq of rank K = 2 form the tensor which characterizes alignment. The form of the probability density in the case where only p and pq are non-zero is presented in Fig. 2.3(c,d,e). The component p characterizes longitudinal alignment, whilst components p x, p 2 characterize transversal alignment. The method of transforming pq on turning the coordinate system is analyzed in Appendix D. 

It is sometimes necessary to analyze the emerging multipole moments (2.21), or, in other cases, the emission intensity (2.24) of light possessing arbitrary polarization and propagating along the direction 0, y>. In this case the cyclic components E , as obtained from (2.6), namely... 

The diagonal elements of the density matrix contain the populations of each of the BO states, whereas off-diagonal elements contain the relative phases of the BO states. The components of the density matrix with a = a describe the vibrational and rotational dynamics in the electronic state a, while the rotational dynamics within a vibronic state are described by the density matrix elements with a = a and va = v ,. The density matrix components with na = n a, describe the angular momentum polarization of the state Ja, often referred to as angular momentum orientation and alignment [40, 87-89]. The density matrix may be expanded in terms of multipole moments as ... 

The spherical form of the multipole expansion is very useful if we are looking for the explicit orientational dependence of the interaction energy. However, in some applications the use the conceptually simpler Cartesian form of the operators V1a 1b may be more convenient. Moreover, unlike the spherical derivation, the Cartesian derivation is very simple, and can be followed by everybody who knows how to differentiate a function of x, y and z 149. To express the operator V,, in terms of Cartesian tensors we have to define the reducible, with respect to SO(3), tensorial components of multipole moments,... 

Here MJ1 denotes the operator of the with spherical component of the multipole moment of order l, and the reaction field moments are given by,... 

The second mechanism is the interaction between the multipole moments induced on A and C by the electrostatic potential of the monomer B. The induction energy component corresponding to this particular interaction will be denoted by ZiLd B C <- B), and can be written as,... 

It includes the interactions of distributed multipole moments Q (up to a quadrupole) labeled t and u. The T matrix provides the Coulomb energy appropriate for particular multipoles and includes the distance between sites a and b and their relative orientations. The short range (penetration) component of the electrostatic energy, in a manner similar to the Ar-CC>2 case, can be absorbed into the exchange repulsion term. 

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