INTRODUCTION OF ATOMIC ORBITALS

What is an Atomic Orbital?

An orbital is the quantum mechanical refinement of Bohr’s orbit. In contrast to his concept of a simple circular orbit with a fixed radius, orbitals are mathematically derived regions of space with different probabilities of having an electron.

One way of representing electron probability distributions was illustrated in Figure 1 for the 1s orbital of hydrogen. Because Ψ2 gives the probability of finding an electron in a given volume of space (such as a cubic picometer), a plot of Ψ2 versus distance from the nucleus (r) is a plot of the probability density. The 1s orbital is spherically symmetrical, so the probability of finding a 1s electron at any given point depends only on its distance from the nucleus. The probability density is greatest at r = 0 (at the nucleus) and decreases steadily with increasing distance. At very large values of r, the electron probability density is very small but not zero.

In contrast, we can calculate the radial probability (the probability of finding a 1s electron at a distance r from the nucleus) by adding together the probabilities of an electron being at all points on a series of x spherical shells of radius r1, r2, r3,…, rx − 1, rx. In effect, we are dividing the atom into very thin concentric shells, much like the layers of an onion (part (a) in Figure 1, and calculating the probability of finding an electron on each spherical shell. Recall that the electron probability density is greatest at r = 0 (part (b) in Figure 1, so the density of dots is greatest for the smallest spherical shells in part (a) in Figure 1. In contrast, the surface area of each spherical shell is equal to 4πr2, which increases very rapidly with increasing r (part (c) in Figure 1. Because the surface area of the spherical shells increases more rapidly with increasing r than the electron probability density decreases, the plot of radial probability has a maximum at a particular distance (part (d) in Figure 1. Most important, when r is very small, the surface area of a spherical shell is so small that the total probability of finding an electron close to the nucleus is very low; at the nucleus, the electron probability vanishes (part (d) in Figure 1.

For the hydrogen atom, the peak in the radial probability plot occurs at r = 0.529 Å (52.9 pm), which is exactly the radius calculated by Bohr for the n = 1 orbit. Thus, the most probable radius obtained from quantum mechanics is identical to the radius calculated by classical mechanics. In Bohr’s model, however, the electron was assumed to be at this distance 100% of the time, whereas in the quantum mechanical Schrödinger model, it is at this distance only some of the time. The difference between the two models is attributable to the wavelike behavior of the electron and the Heisenberg uncertainty principle.

Figure 2 compares the electron probability densities for the hydrogen 1s, 2s, and 3s orbitals. Note that all three are spherically symmetrical. For the 2s and 3s orbitals, however (and for all other s orbitals as well), the electron probability density does not fall off smoothly with increasing r. Instead, a series of minima and maxima are observed in the radial probability plots (part (c) in Figure 2. The minima correspond to spherical nodes (regions of zero electron probability), which alternate with spherical regions of nonzero electron probability.