Radial Probabilities

Radial Probability: probability of finding the electron at a distance between r and r + dr

from the nucleus.
In general, nlm (r, , ) = Radial Part x Angular Part
Rnl (r)

lm (, )

Radial Probability = Radial Probability Density x Volume

Thus to get the Radial Probability we must specify the Radial Probability Density and the
Volume
2

Radial Probability Density = Rnl (r) : Square of the Radial Wavefunction

The required volume is determined by the volume of the SPHERICAL SHELL enclosed
between a sphere of radius (r+dr) and a sphere of radius r (see figure).

4r2R2nl(r) is called a Radial Probability DISTRIBUTION. Thus the figure below and a
similar one in your text are plots of Radial Probability Distributions.

General result: Area under curve between r1 and r1+dr = Probability of finding e- between
r1 and r1 + dr.
Important points to note about the (4)r2R2 vs. r plots:
i) Radial probability is ALWAYS SMALL near the nucleus {4r2 small near the nucleus}.
ii) The maximum in the 4r2R21s vs. r plot occurs at 0.53 - just the radius of the n=1 orbit
of the Bohr model.
iii) On the average a 2s electron spends its time a greater distance from the nucleus than the
1s electron - consistent with the observation that 2s > 1s.
iv) The position of the principal (i.e., largest) maximum depends on n and l. For fixed l, as
n the position of the principal maximum moves to larger r values. (For fixed n, the
position of the principal maximum moves to shorter r values as l .)
i.e., (r2p)max < (r2s)max ; (r3d)max < (r3p)max < (r3s)max
v) An n s-electron has a greater probability of being very close to the nucleus than does an
n p-electron; an n p-electron has a greater probability of being closer to the nucleus than
does an n d-electron etc. These data may be summarized as an ability to penetrate to the
nucleus.
Penetration ability For FIXED n: s > p > d > f - this is important for a discussion
of the periodic table and ionization energies.