Van der Waals Interactions Are Caused by Transient Dipoles

When any two atoms approach each other closely, they create a weak, nonspecific attractive force called a van der Waals interaction. These nonspecific interactions result from the momentary random fluctuations in the distribution of the electrons of any atom, which give rise to a transient unequal distribution of electrons. If two noncovalently bonded atoms are close enough together, electrons of one atom will perturb the electrons of the other. This perturbation generates a transient dipole in the second atom, and the two dipoles will attract each other weakly (Figure 2-8). Similarly, a polar covalent bond in one molecule will attract an oppositely oriented dipole in another.

Van der Waals interactions, involving either transiently induced or permanent electric dipoles, occur in all types of molecules, both polar and nonpolar. In particular, van der Waals interactions are responsible for the cohesion between molecules of nonpolar liquids and solids, such as heptane, CH3—(CH2)5—CH3, that cannot form hydrogen bonds or ionic interactions with other molecules. The strength of van der Waals interactions decreases rapidly with increasing distance; thus these noncovalent bonds can form only when

▲ FIGURE 2-7 Distribution of bonding and outer non-bonding electrons in the peptide group. Shown here is one amino acid within a protein called crambin. The black lines diagrammatically represent the covalent bonds between atoms. The red (negative) and blue (positive) lines represent contours of charge. The greater the number of contour lines, the higher the charge. The high density of red contour lines between atoms represents the covalent bonds (shared electron pairs). The two sets of red contour lines emanating from the oxygen (O) and not falling on a covalent bond (black line) represent the two pairs of nonbonded electrons on the oxygen that are available to participate in hydrogen bonding. The high density of blue contour lines near the hydrogen (H) bonded to nitrogen (N) represents a partial positive charge, indicating that this H can act as a donor in hydrogen bonding. [From C. Jelsch et al., 2000, Proa. Nat'l. Acad. Sci. USA 97:3171. Courtesy of M. M. Teeter.]

▲ FIGURE 2-8 Two oxygen molecules in van der Waals contact. In this space-filling model, red indicates negative charge and blue indicates positive charge. Transient dipoles in the electron clouds of all atoms give rise to weak attractive forces, called van der Waals interactions. Each type of atom has a characteristic van der Waals radius at which van der Waals interactions with other atoms are optimal. Because atoms repel one another if they are close enough together for their outer electrons to overlap, the van der Waals radius is a measure of the size of the electron cloud surrounding an atom. The covalent radius indicated here is for the double bond of O=O; the singlebond covalent radius of oxygen is slightly longer.

atoms are quite close to one another. However, if atoms get too close together, they become repelled by the negative charges of their electrons. When the van der Waals attraction between two atoms exactly balances the repulsion between their two electron clouds, the atoms are said to be in van der Waals contact. The strength of the van der Waals interaction is about 1 kcal/mol, weaker than typical hydrogen bonds and only slightly higher than the average thermal energy of molecules at 25 °C. Thus multiple van der Waals interactions, a van der Waals interaction in conjunction with other nonco-valent interactions, or both are required to significantly influence intermolecular contacts.

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