|Themes > Science > Chemistry > Inorganic Chemistry > More Information about Chemical Bonding > The electron-tunneling model of chemical bonding|
Chemical bonding occurs when one or more electrons can be simultaneously close to two nuclei. But how can this be arranged? The conventional picture of the shared electron bond places the bonding electrons in the region between the two nuclei. This makes a nice picture, but it is not consistent with the principle that the most energetically favorable place for electrons is very close to a nucleus, not half a bond-length away from two of them.
When an elecron is added to the proton to make a neutral hydrogen atom, it tries to get as close to the nucleus as possible. The Heisenberg Indeterminancy ("uncertainty") principle requires the total energy of the electron energy to increase as the volume of space it occupies diminishes. As the electron gets closer to the nucleus, the nuclear charge confines the electron to such a tiny volume of space that its energy rises, allowing it to "float" slightly away from the nucleus without ever falling into it.
The shaded region shows the range of energies and distances from the nucleus the electron is able to assume within the 1s orbital. The electron can thus be regarded as a fluid that occupies a vessel whose walls conform to the red potential energy curves shown above. Note that as the potential energy falls, the kinetic energy increases, but only half as fast (this is called the "Virial Theorem".). Thus close to the nucleus, the kinetic energy is large and so is the electron's effective velocity. The top of the shaded area defines the work required to raise its potential energy to zero, thus removing it from the atom; this corresponds, of course, to the ionization energy.
Suppose we bring a bare proton up close to a hydrogen atom. Each nucleus has its own potential well, but only that of the hydrogen atom is filled.
But the electron fluid is able to tunnel through the potential energy barrier separating the two wells; like any liquid, it will seek a common level in the two sides of the container. The electron is now "simultaneously cose to two nuclei" while never being in between them. Bear in mind that this would be physically impossible for a real liquid composed of real molecules; this is purely a quantum effect that is restricted to a low-mass particle such as the electron.
Because the same amount of electron fluid is now shared between the two wells, its level in both is lower. The difference between what it is now and what is was before corresponds to the bond energy of the hydrogen molecule ion.
Now let's make a molecule of dihydrogen. We start with two hydrogen atoms, each with one electron. But there is a problem here: both potential energy wells are already filled with electron fluid; there is no room for any more without pushing the energy way up. But quantum theory again comes to the rescue! If the two electrons have opposite spins, the two fluids are able to interpenetrate each other, very much as two gases are able to occupy the same container.
When the two hydrogen atoms are within tunneling distance, half of the electron fluid (really the probabability of finding the electron) from each well flows into the other well. Because the two fluids are able to interpenetrate, the level is not much different from what it was in the H22 ion; H2 is therefore a strongly bound molecule.
If we tried to join two helium atoms in this way, we would be in trouble. The electron well of He already contains two electrons of opposite spin. There is no room for more electron fluid (without raising the energy), and thus no way the electrons in either He atom can be simultaneously close to two nuclei.