Molecular structure intermolecular forces

Intermolecular forces are the attractive forces that hold molecules and ions together. These forces should not be confused with the intramolecular forces that hold the atoms together in a covalent molecule (see Lesson 11, Molecular Structure ). Intermolecular forces are grouped into four classifications, each supporting the existence of the condensed states of matter solids and liquids. In addition, these forces can also explain the nonideal behavior of certain gases. 

To provide a more quantitative explanation of the magnitudes of the properties of different materials, we must consider several types of intermolecular forces in greater detail than we gave to the Lennard-Jones model potential in Chapter 9. The Lennard-Jones potential describes net repulsive and attractive forces between molecules, but it does not show the origins of these forces. We discuss other intermolecular forces in the following paragraphs and show how they arise from molecular structure. Intermolecular forces are distinguished from intramolecular forces, which lead to the covalent chemical bonds discussed in Chapters 3 and 6. Intramolecular forces between atoms in the covalent bond establish and maintain... 

The study of the rotation-vibration spectra of polyatomic molecules in the gas phase can provide extensive information about the molecular structure, the force field and vibration-rotation interaction parameters. Such IR-spectra are sources of rotational information, in particular for molecules with no permanent dipole moment, since for these cases a pure rotational spectrum does not exist. Vibrational frequencies from gas phase spectra are desirable, because the molecular force field is not affected by intermolecular interactions. Besides, valuable support for the assignment of vibrational transitions can be obtained from the rotational fine structure of the vibrational bands. Even spectra recorded with medium resolution can contain a wealth of information hot bands , for instance, provide insight into the anharmonicity of vibrational potentials. Spectral contributions of isotopic molecules, certainly dependent on their abundance, may also be resolved. 

One cannot decide on a preference between the favorable sc or ap conformations on an a priori basis. These two cases must be distinguished by experiments, usually by measuring coupling constants in HNMR spectra (see Fig. 1.2.14). X-ray analysis is of limited use, since crystal forces often enforce linear conformations of polyfunctional chains, which are not found in solution or in noncrystalline molecular assemblies. Intermolecular forces are invariably more important in crystals than in curved supramolecular structures. 

During the early years of this century, organic chemists were enjoying success in determining the structures of ordinary-sized organic molecules, and this probably contributed to their reluctance to look beyond structures of convenient size. Physical chemists were interested in intermolecular forces at this period, and the idea that polymers were the result of some sort of association between low molecular weight constituent molecules prevailed fora long while. 

In the last decade two-dimensional (2D) layers at surfaces have become an interesting field of research [13-27]. Many experimental studies of molecular adsorption have been done on metals [28-40], graphite [41-46], and other substrates [47-58]. The adsorbate particles experience intermolecular forces as well as forces due to the surface. The structure of the adsorbate is determined by the interplay of these forces as well as by the coverage (density of the adsorbate) and the temperature and pressure of the system. In consequence a variety of superstructures on the surfaces have been found experimentally [47-58], a typical example being the a/3 x a/3- structure of adsorbates on a graphite structure (see Fig. 1). 

We have to refine our atomic and molecular model of matter to see how bulk properties can be interpreted in terms of the properties of individual molecules, such as their size, shape, and polarity. We begin by exploring intermolecular forces, the forces between molecules, as distinct from the forces responsible for the formation of chemical bonds between atoms. Then we consider how intermolecular forces determine the physical properties of liquids and the structures and physical properties of solids. 

What Do We Need to Know Already It would be a good idea to review the information on periodic trends in Sections 1.15-1.22 and 14.1-14.2. Because the nonmetals form molecular compounds, it would also be helpful to review Lewis structures, electronegativity, and covalent bonding in Chapters 2 and 3. The bulk properties of nonmetallic materials are affected by intermolecular forces (Sections 5.1-5.5). 

Finally, there are groups of liquid crystals where, at the current time, force fields are not particularly useful. These include most metal-containing liquid crystals. Some attempts have been made to generalise traditional force fields to allow them to cover more of the periodic table [40, 43]. However, many of these attempts are simple extensions of the force fields used for simple organic systems, and do not attempt to take into account the additional strong polarisation effects that occur in many metal-containing liquid crystals, and which strongly influence both molecular structure and intermolecular interactions. 

Molecular solids are aggregates of molecules bound together by intermolecular forces. Substances that are gases under normal conditions form molecular solids when they condense at low temperature. Many larger molecules have sufficient dispersion forces to exist as solids at room temperature. One example is naphthalene (Cio Hg), a white solid that melts at 80 °C. Naphthalene has a planar structure like that of benzene (see Section 10-), with a cloud of ten delocalized n electrons that lie above and below the molecular plane. Naphthalene molecules are held in the solid state by strong dispersion forces among these highly polarizable n electrons. The molecules in... 

Hybrid MPC-MD schemes may be constructed where the mesoscopic dynamics of the bath is coupled to the molecular dynamics of solute species without introducing explicit solute-bath intermolecular forces. In such a hybrid scheme, between multiparticle collision events at times x, solute particles propagate by Newton s equations of motion in the absence of solvent forces. In order to couple solute and bath particles, the solute particles are included in the multiparticle collision step [40]. The above equations describe the dynamics provided the interaction potential is replaced by Vj(rJVs) and interactions between solute and bath particles are neglected. This type of hybrid MD-MPC dynamics also satisfies the conservation laws and preserves phase space volumes. Since bath particles can penetrate solute particles, specific structural solute-bath effects cannot be treated by this rule. However, simulations may be more efficient since the solute-solvent forces do not have to be computed. 

These models are semiempirical and are based on the concept that intermolecular forces will cause nonrandom arrangement of molecules in the mixture. The models account for the arrangement of molecules of different sizes and the preferred orientation of molecules. In each case, the models are fitted to experimental binary vapor-liquid equilibrium data. This gives binary interaction parameters that can be used to predict multicomponent vapor-liquid equilibrium. In the case of the UNIQUAC equation, if experimentally determined vapor-liquid equilibrium data are not available, the Universal Quasi-chemical Functional Group Activity Coefficients (UNIFAC) method can be used to estimate UNIQUAC parameters from the molecular structures of the components in the mixture3. 

Scrocco, E., and J. Tomasi. 1978. Electronic Molecular Structure, Reactivity and Intermolecular Forces A Heuristic Interpretation by Means of Electrostatic Molecular Potentials. Adv. Quant. Chem. 11,115. 

Using molecular structures and principles of intermolecular forces, explain why liquid BrF3 has a viscosity that is approximately three times that of BrFs at a temperature of 20 0 C. 

Choices A, B, C, and D involve the strength of intermolecular forces. Because the two compounds differ in structure, there would be intermolecular differences between the two compounds. However, because both isomers have the same molecular mass, they would have the same gas density. 

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