Dipole interacting

The gradient model for interfacial tension described in Eqs. III-42 and III-43 is limited to interaction potentials that decay more rapidly than r. Thus it can be applied to the Lennard-Jones potential but not to a longer range interaction such as dipole-dipole interaction. Where does this limitation come from, and what does it imply for interfacial tensions of various liquids ... 

Stigter and Dill [98] studied phospholipid monolayers at the n-heptane-water interface and were able to treat the second and third virial coefficients (see Eq. XV-1) in terms of electrostatic, including dipole, interactions. At higher film pressures, Pethica and co-workers [99] observed quasi-first-order phase transitions, that is, a much flatter plateau region than shown in Fig. XV-6. 

Consider the interaction of a neutral, dipolar molecule A with a neutral, S-state atom B. There are no electrostatic interactions because all the miiltipole moments of the atom are zero. However, the electric field of A distorts the charge distribution of B and induces miiltipole moments in B. The leading induction tenn is the interaction between the pennanent dipole moment of A and the dipole moment induced in B. The latter can be expressed in tenns of the polarizability of B, see equation (Al.S.g). and the dipole-mduced-dipole interaction is given by... 

If molecule A is a linear, spherical or synnnetric top that has a zero dipole moment like benzene, then the leading induction tenn is the quadnipole-mduced-dipole interaction... 

Note the r dependence of these tenns the charge-indiiced-dipole interaction varies as r, the dipole-indiiced-dipole as and the quadnipole-mduced-dipole as In general, the interaction between a pennanent 2 -pole moment and an induced I -pole moment varies as + L + l) gQ enough r, only the leading tenn is important, with higher tenns increasing in importance as r decreases. The induction forces are clearly nonadditive because a third molecule will induce another set of miiltipole moments in tlie first two, and these will then interact. Induction forces are almost never dominant since dispersion is usually more important. 

In the third order of long-range perturbation theory for a system of tluee atoms A, B and C, the leading nonadditive dispersion temi is the Axilrod-Teller-Mutd triple-dipole interaction [58, 59]... 

Themiodynamic stability requires a repulsive core m the interatomic potential of atoms and molecules, which is a manifestation of the Pauli exclusion principle operating at short distances. This means that the Coulomb and dipole interaction potentials between charged and uncharged real atoms or molecules must be supplemented by a hard core or other repulsive interactions. Examples are as follows. 

At distances of a few molecular diameters, the interaction will be dominated by electric multipole interactions for dipolar molecules, such as water, the dominant tenn will be the dipole-dipole interaction ... 

This fomuila does not include the charge-dipole interaction between reactants A and B. The correlation between measured rate constants in different solvents and their dielectric parameters in general is of a similar quality as illustrated for neutral reactants. This is not, however, due to the approximate nature of the Bom model itself which, in spite of its simplicity, leads to remarkably accurate values of ion solvation energies, if the ionic radii can be reliably estimated [15],... 

With this convention, we can now classify energy transfer processes either as resonant, if IA defined in equation (A3.13.81 is small, or non-resonant, if it is large. Quite generally the rate of resonant processes can approach or even exceed the Leimard-Jones collision frequency (the latter is possible if other long-range potentials are actually applicable, such as by pennanent dipole-dipole interaction). 

Resonant rotational to rotational (R-R) energy transfer may have rates exceeding the Leimard-Jones collision frequency because of long-range dipole-dipole interactions in some cases. Quasiresonant vibration to rotation transfer (V-R) has recently been discussed in the framework of a simple model [57]. 

We now come back to the important example of two spin 1/2 nuclei with the dipole-dipole interaction discussed above. In simple physical tenns, we can say that one of the spins senses a fluctuating local magnetic field originatmg from the other one. In tenns of the Hamiltonian of equation B 1.13.8. the stochastic fiinction of time F l t) is proportional to Y2 (9,( ))/rjo, where Y, is an / = 2 spherical hannonic and r. is the... 

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... 

If the collision starts on the excited level, the long-range dipole-dipole interaction produces an interatomic... 

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)). 

Electrostatic terms other than the simple charge interactions above are commonly included in molecular mechanics calculations. particularly dipole-dipole interactions. More recently, second-order electrostatic interactions like those describing polarizability have been added to some force fields. 

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