Multipole moments

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... 

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] ... 

The electrostatic potential generated by a molecule A at a distant point B can be expanded m inverse powers of the distance r between B and the centre of mass (CM) of A. This series is called the multipole expansion because the coefficients can be expressed in temis of the multipole moments of the molecule. With this expansion in hand, it is... 

The polarization interaction arises from the interaction between the ion of charge Ze and the multipole moments it induces in the atom or molecule AB. The dominant polarization interaction is the ion-mduced dipole interaction... 

The electrostatic interaction results from the interaction of tire ion with the pennanent multipole moments of the neutral. For cylindrically synnnetric neutrals or linear molecules, the ion-neutral multipole interaction is... 

The anisotropy of the product rotational state distribution, or the polarization of the rotational angular momentum, is most conveniently parametrized tluough multipole moments of the distribution [45]. Odd multipoles, such as the dipole, describe the orientation of the angidar momentum /, i.e. which way the tips of the / vectors preferentially point. Even multipoles, such as the quadnipole, describe the aligmnent of /, i.e. the spatial distribution of the / vectors, regarded as a collection of double-headed arrows. Orr-Ewing and Zare [47] have discussed in detail the measurement of orientation and aligmnent in products of chemical reactions and what can be learned about the reaction dynamics from these measurements. 

Task 1 Calculate the first non-vanishing multipole moment of the electrostatic potential of composed objects (i.e., structural units and clusters). 

The raie gas atoms reveal through their deviation from ideal gas behavior that electrostatics alone cannot account for all non-bonded interactions, because all multipole moments are zero. Therefore, no dipole-dipole or dipole-induced dipole interactions are possible. Van der Waals first described the forces that give rise to such deviations from the expected behavior. This type of interaction between two atoms can be formulated by a Lennaid-Jones [12-6] function Eq. (27)). 

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. 

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. 

A central multipole expansion therefore provides a way to calculate the electrostatic interaction between two molecules. The multipole moments can be obtained from the wave-function and can therefore be calculated using quantum mechanics (see Section 2.7.3) or can be determined from experiment. One example of the use of a multipole expansion is... 

Fowler P W and A D Buckingham 1991. Central or Distributed Multipole Moments Electrostatic Models of Aromatic Dimers. Chemical Physics Letters 176 11-18. 

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 Onsager model describes the system as a molecule with a multipole moment inside of a spherical cavity surrounded by a continuum dielectric. In some programs, only a dipole moment is used so the calculation fails for molecules with a zero dipole moment. Results with the Onsager model and HF calculations are usually qualitatively correct. The accuracy increases significantly with the use of MP2 or hybrid DFT functionals. This is not the most accurate method available, but it is stable and fast. This makes the Onsager model a viable alternative when PCM calculations fail. 

The molecular dipole moment is perhaps the simplest experimental measure of charge density in a molecule. The accuracy of the overall distribution of electrons in a molecule is hard to quantify, since it involves all of the multipole moments. Experimental measures of accuracy are necessary to evaluate results. The values for the magnitudes of dipole moments from AMI calculations for a small sample of molecules (Table 4) indicate the accuracy you may... 

The two-center two-electron repulsion integrals ( AV Arr) represents the energy of interaction between the charge distributions at atom Aand at atom B. Classically, they are equal to the sum over all interactions between the multipole moments of the two charge contributions, where the subscripts I and m specify the order and orientation of the multipole. MNDO uses the classical model in calculating these two-center two-electron interactions. 

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. 

Molecular energies and structures Energies and structures of transition states Bond and reaction energies Molecular orbitals Multipole moments... 

Multipole moments are useful quantities in that they collectively describe an overall charge distribution. In Chapter 0, I explained how to calculate the electrostatic field (and electrostatic potential) due to a charge distribution, at an arbitrary point in space. 

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