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Too Many Electrons

What happens to electron pairs which are left over after all bonds have been formed? Is each electron pair primarily associated with a single atom and directed tetrahedrally from this atom as implied by Lewis structures, or is it spread out? Are these extra pairs (lone pairs) just hangers on, or do they contribute to (or even dominate) the chemistry. In this activity you will examine molecules with too many electrons (the exact opposite you did in the previous activity Too Few Electrons). You will use electrostatic potential surfaces to probe where these extra (non-bonded) electrons reside and try to associate what you find with conventional (Lewis) structures. 1. Build ammonia, water and hydrogen fluoride, and put them in the same document. Request equilibrium geometries using the HF/ 6-31G* model. Before you submit for calculation, also request calculation of electrostatic potential surfaces for the three molecules. The requested isosurfaces correspond to an electrostatic potential isovalue of -80 kJ/mol. These will demark the highly electron-rich regions for the three molecules. After the calculations have completed, display all three potential surfaces side-by-side on screen.
Bring up the spreadsheet. For Windows, check the box to the right of the first (Label) column for each molecule. For Mac, click on at the bottom left of the screen and check the box to the left of the molecule name (in the spreadsheet) for each molecule. You also need to select (uncheck) Coupled from the Model menu in order to uncouple the motions of the three molecules so that you can move them independently.

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Describe the three surfaces and relate them to the conventional Lewis structures.
N H O H H H H F H

In this context, rationalize the unusual shape of the potential for water. Also, elaborate and rationalize the difference in the shapes of the ammonia and hydrogen fluoride potentials (which at first glance appear to be nearly identical). 2. Revisit the isoelectronic series, methyl anion, ammonia and hydronium cation (see the activity How Big are Atoms and Molecules?).
If you have performed this earlier activity, you dont need to build and optimize these molecules a second time, but only compute electrostatic potential surfaces.

Display the three potential surfaces side-by-side on screen. For which does the potential extend furthest away from the nuclei? For which is the extension the least? Does this correlate with the sizes of the electron densities (see previous activity)? What do the relative sizes (extensions) of the potential tell you about the relative likelihood of these three molecules to act as electron sources (nucleophiles)? 3. Hydrazine, N2H4, is a very high-energy molecule and is used as a rocket fuel. Like ethane, it should prefer a staggered arrangement of hydrogens (see the essay Potential Energy Surfaces). The difference is that two of the CH bonds in ethane have been replaced by electron pairs in hydrazine. A consequence of this is that there are two staggered arrangements, one with the electron pairs anti and the other with the electron pairs gauche.
H H anti hydrazine N N H H H H H N N H

gauche hydrazine

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On the basis of the same arguments made in VSEPR theory (electron pairs take up more space than bonds) you might expect that anti hydrazine would be the preferred structure. Here, you will use quantum chemical calculations to test your intuition. Build both anti and gauche hydrazine and put into the same document. Request equilibrium geometries using the HF/6-31G* model. Also request calculation of electrostatic potential surfaces.
With hydrazine on screen (in the builder), you can rotate about the NN bond by first clicking on it (a red arrow will ring the bond; if the ring disappears, click again), and then moving the mouse up and down with both the Alt key (space bar for the Mac) and left button depressed. Rotate into the proper (anti or gauche) structure and then select Minimize from the Build menu to give a better geometry. The anti structure will have C2h symmetry and the gauche structure will have C2 symmetry.

After the calculations have completed, examine the energies for the two molecules. Which is favored? By how much? Is this result in accord with what you would expect from VSEPR theory?
The energy will be given in atomic units (au). To convert to kJ/mol, multiply by 2625. The HOMO energy (in eV) which will be needed below is also available in this dialog. To convert from eV (electron volts) to kJ/mol, multiply by 96.49.

Examine the two potential surfaces side-by-side on screen. Is there a noticeable difference in the extent to which the two electron pairs interact (delocalize) between the two conformers? If so, is the more delocalized conformer lower or higher in energy than the less delocalized conformer? You can rationalize your result by recognizing that when electron pairs interact they form combinations, one of which is stabilized (relative to the original electron pairs) and one of which is destabilized. Destabilization is greater than stabilization, meaning that overall interaction of two electron pairs is unfavorable energetically.

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destabilized combination HOMO

stabilized combination

In terms of molecular orbital theory, the higher-energy (destabilized) combination of electron pairs is the HOMO. You can judge the extent to which the electron pairs interact (and the overall destabilization) by measuring the energy of the HOMO. Which hydrazine conformer has the higher HOMO energy? Is this the higher-energy conformer? If so, is the difference in HOMO energies similar to the energy difference between conformers?

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