Understanding the Hydrogenic orbital expressions

Prashant U. Manohar
Department of Chemistry, Birla Institute of Technology and Science, Pilani, Rajasthan 333031

August 25, 2014

The purpose of this tutorial is to learn to correlate the hydrogenic orbital expressions with the nomenclature
or the symbols of the orbitals. The orbital analysis that we plan to do here requires only the qualitative
knowledge of the orbital expressions. For detailed study of quantitative aspects (like, for example, exact value
of most probable radius, exact position(s) of radial node(s), etc.), one has to go for a more rigorous treatement
- the detailed study of exact solution of the time-independent Schrodinger equation for hydrogenic atoms,
which is beyond the scope of present discussion. In the spherical polar coordinate system (which is the most
natural choice of coordinate system for studying a hydrogenic atom) the Schrodinger equation simplifies on
variable separation treatment into azimuthal wave-equation, polar wave-equation and radial wave-equation,
respectively.
The symbol of the hydrogenic orbital consists of three parts, the principle quantum number, n, followed
by the spectroscopic symbol for the azimuthal quantum number, l (The symbols s, p, d, f, g, h, i, ... belong to
l = 0, 1, 2, 3, 4, 5, 6, ..., respectively), followed by a subscript which will be related to the magnetic quantum
number in some sense. The orbital expressions are strongly dependent on these quantum numbers. The aim
of this tutorial is, thus, to understand how to find these quantum numbers from the orbital expressions and
hence, how to name the orbital.
An orbital expression has mainly two parts: the Radial wavefunction and the Angular wavefunction (spherical harmonics). Well study both these parts and learn how to characterize the orbitals from the mathematical
expressions.

Radial wavefunctions

The radial wavefunction is represented by Rn,l (r) as it is a function of r and depends on the quantum numbers,
n and l. The azimuthal quantum number, l (also known as orbital angular momentum quantum number),
is actually introduced in the polar wave-equation. The solution of the radial wave-equation introduces the
principle quantum number, n, which in turn imposes a limit on maximum value of l. The principle quantum
number can take only positive integer values (n = 1, 2, 3, ....), whereas the azimuthal quantum number take
the non-negative integer values up to n 1, that is, l = 0, 1, ...n 1. The radial wavefunction Rn,l (r) has the

following general form.

nl1
X

(1)j aj rj eZr/na0

Rn,l (r) = N rl

(1)

j=0

In the above expression, N is the normalization factor, which, in general, is different for different orbitals. In
principle, rl could have been absorbed in the polynomial and we could have written the radial wavefunction
as

n1
X

(1)jl aj rj eZr/na0

Rn,l (r) = N

(2)

j=l

Although, the form given by Eq (2) looks more compact, the form in Eq (1) is more instructive for orbital
characterization. The rl term gives us the value of the azimuthal quantum number l which is equal to the
number of the angular nodes in the orbital. The bracket contains the polynomial of degree n l 1 in r and
must have the terms starting from r0 to rnl1 . The coefficients aj s are all positive real coefficients and (1)j
ensures that alternate terms in the expression (in particular, the terms with odd powers of r) will be negative.
Being the polynomial of degeree n l 1, it has n l 1 roots, each of which corresponds to a radial node.
Thus, the total number of nodes in the orbital is l plus n l 1 which equals to n 1. The principle quantum
number n can also be obtained from the third part of the expression, that is, the exponential term, which has
na0 in the denominator of the exponent.
One can also use these facts to check whether the orbital expression is logically correct from whether the
value of n is in the exponential term is consistent with the degree of the polynomial and l. As the information
about the quantum numbers n and l is completely obtainable from radial part of the wavefunction, one can
correctly determine the sub-shell to which the orbital belongs, just from the radial wavefunction. We will now
see the radial wavefunctions of some orbitals.
R1,0

= N eZr/a0

(3)

R2,0

= N (2 Zr/a0 ) eZr/2a0

(4)

R2,1

= N reZr/2a0

(5)

R3,0

= N 27 18(Zr/a0 ) + 2(Zr/a0 )2 eZr/3a0

(6)

R3,1

= N r (6 Zr/a0 ) eZr/3a0

(7)

R3,2

= N r2 eZr/3a0

(8)
eZr/4a0

R4,1

= N 192 144(Zr/a0 ) + 24(Zr/a0 )2 (Zr/a0 )

= N r 80 20(Zr/a0 ) + (Zr/a0 )2 eZr/4a0

R4,2

N r2 (12 Zr/a0 ) eZr/4a0

(11)

R4,3

N r3 eZr/4a0

(12)

R4,0

3

(9)
(10)

The following points are to be noted and understood in the above expressions.
The equations (3,4, 6 and 9) correspond to s-type orbitals. Since, l = 0 for these orbitals, the rl
term doesnt appear in these expressions. The equations (5,7 and 10) correspond to p-type orbitals
2

(characterised by l = 0) and have a term r (that is, r1 ). Similarly, the equations (8 and 11) correspond
to d-type orbitals and have r2 dependence corresponding to l = 2. The equation (12) corresponds to
an f -type orbital and has r3 dependence as l = 3. (The l = 0, 1, 2, 3, 4, 5, 6, ... are characterized by
spectroscopic symbols, s, p, d, f, g, h, i, ..., respectively).
The orbitals of the subshells, 1s, 2p, 3d and 4f will have no radial nodes as nl 1 = 0 for these orbitals.
Therefore, no polynomial in r is found in the equations (3, 5, 8 and 12). The equations (4, 8 and 11)
correspond to 2s, 3p and 4d the subshells with each orbital having only one radial node and hence, have
a linear polynomial in r corresponding to n l 1 = 1. The orbitals of the 3s and 4p subshells have two
radial nodes corresponding to n l 1 = 2 and are characterized by the quadratic polynomial in r in
the equations (6 and 10). The 4s orbital has n l 1 = 3, that is, three radial nodes and consequently,
a cubic polynomial in r as seen in the equation (9).
The polynomial terms with odd powers of r are all negative while the rest are all positive. The magnitude
of the coefficients decreases with increase in the power of (Zr/a0 ). This ensures distinct positive roots
of the polynomials.
The total number of nodes (n 1) is equal to the number of angular nodes (l) and the number of radial
nodes (n l 1). The values of l in rl and of n in eZr/na0 are consistent with the degree (n l 1) of
the respective polynomials.

Angular wavefunctions

The angular wavefunctions of the hydrogenic orbitals are called spherical harmonics and can also be obtained
as eigenfunctions of the orbital angular momentum squared operator. These are represented by Yl,ml (, ) and
are expressible as product of pure functions of and , respectively.
Yl,ml (, ) = l,ml ()ml ()

(13)

The functions ml () is obtained on solving the azimuthal wave-equation, which is obtained by separating
the -dependent terms from the rest of the Schrodinger equation. The azimuthal wave-equation is identical
to the Schr
odinger equation for particle on a ring and the eigenfunctions are

1
ei|ml | ,
(2)1/2

where ml is an

integer. The lower and upper bounds to ml are actually imposed upon solving the -dependent part (polar
wave-equation) of the Schr
odinger equation, where the azimuthal quantum number l is introduced. The polar
wavefunctions are the normalized associated Legendre polynomials of degree l expressed in terms of cos and
sin. The polar wavefunction for l = 0 states is (non-zero) constant. For the orbitals with ml = 0, since the
orbital angular momentum is oriented in xy-plane (z-component is zero), there is no dependence on and the
polar wavefunction is a pure polynomial in cos. For all other orbitals, the polar wavefunction is multipled
by an azimuthal (-dependent) wavefunction. The polar wavefunction for such orbitals is a single term (or a
polynomial of rank l with the highest power term) expressible as cosj sinlj , where, j = 0, .., l.
3

The solution of the polar wave-equation is somewhat involved and as far as the General Chemistry course
is concerned, we wont worry about how-to-solve-it. We will rather only study how to use those solutions.
Based on the form of the angular wavefunctions, we divide the orbitals into three sub-sets:
(1) Orbitals with l = 0.
(2) Orbitals with l > 0 and ml =0.
(3) Orbitals with l > 0 and ml 6= 0.
The orbitals belonging to the subset (1) are the s-orbitals. Being -independent as well as -independent
(since, Y0,0 (, ) = (non-zero) constant), they are spherically symmetric. These orbitals can thus, be completely
identified from the radial part alone and are named as ns, where n is the principle quantum number. They
represent the atomic states corresponding to zero orbital angular momentum (since l = 0) and exactly known
energy.
1s

= M eZr/a0

(14)

2s

= M (2 Zr/a0 ) eZr/2a0

(15)

3s

= M 27 18(Zr/a0 ) + 2(Zr/a0 )2 eZr/3a0

(16)

4s

= M 192 144(Zr/a0 ) + 24(Zr/a0 )2 (Zr/a0 )3 eZr/4a0

(17)

In the above orbital expressions (and the orbital expressions hereafter), M is normalization constant, and is, in
general, different for different orbitals. The subset (2) refers to the orbitals with ml = 0. These orbitals have
maximum probability density oriented along z-direction and are are named as n(spectroscopic symbol for
l)zl , for example, 2pz , 3pz , 3dz2 , 4pz , 4dz2 , 4fz3 , 5gz4 , and so on. Optionally, since ml = 0 for these orbitals,
zero is used in the subscript instead of zl , for example, 2p0 , 3p0 , 3d0 , and so on. These orbitals represent
the atomic states for which energy and magnitude of the orbital angular momentum can be exactly known.
The z-component of the orbital angular momentum for these states is zero, indicating that the orbital angular
momentum vector lies in xy-plane.
2pz or 2p0

= M reZr/2a0 cos

(18)

3pz or 3p0

= M r (6 Zr/a0 ) eZr/3a0 cos

(19)

3dz2 or 3d0
4pz or 4p0

= M r2 eZr/3a0 (3cos2 1)
= M r 80 20(Zr/a0 ) + (Zr/a0 )

(20)


2

eZr/4a0 cos

(21)

4dz2 or 4d0

= M r2 (12Zr/a0 ) eZr/4a0 (3cos2 1)

(22)

4fz3 or 4f0

= M r3 eZr/4a0 (5cos3 3cos)

(23)

In the above expressions, note the rl factor from the radial part and the cosl term in the angular part. The
rl cosl equals (rcos)l which equals z l . Thus, the z l in the subscripts of the orbital-symbols above have a
physically meaningful interpretation. If one wants to be more rigorous, the full polynomial in cos may be
4

considered and one must write the symbols for the the orbitals as 2pz , 3pz , 3d3z2 r2 , 4d3z2 r2 , 4f5z3 3zr2 , and
so on.
The orbitals with l 6= 0 and non-zero ml belong to the subset (3). There are two interconvertable subsets
of this type and one can choose any one of these, but not both, simultaneously, depending on the requirement.
This statement will be clear shortly. For convenience, we label the two subsets as (3A) and (3B).
The orbitals corresponding to subset (3A) have exactly known ml are characterized by eiml . Like the
orbitals of subsets (1 and 2), these orbitals represent the atomic states with magnitude and the z-component
of the orbital angular momentum exactly known in addition to the energy. These orbitals are named as
n(spectroscopic symbol for l)ml , for example, 2p+1 , 2p1 , 3d2 , 4f+3 , etc.
2p1

= M reZr/2a0 sinei

(24)

3d1

= M r2 eZr/3a0 sin2ei

(25)

3d2

= M r2 eZr/3a0 sin2 e2i

(26)

The maximum probability density of these orbitals is oriented off-the z-axis, but along which direction(s),
cannot be determined. Thus, if one wants to study the properties that are strongly responsive to orientation
in three dimensional space, this set of orbitals is poor in obtaining such information.
However, instead of considering the orbitals of this subset as such, one can choose to take linear combination
of each orbital-pair corresponding to a ml value (ml 6= 0) and obtain the new orbital-pairs for which the
orientation(s) of the maximum probability density can be identified. However, the ml value becomes uncertain
in terms of the sign. For convenience, we will call these linearly combined orbitals as orientation-expressive
orbitals.
The orientation-expressive orbitals constitute the subset (3B) and are still, the eigen-functions of the
Hamiltonian operator as well as of the angular momentum squared operator. Therefore, these correspond
to the atomic states with exactly known magnitude of orbital angular momentum in addition to the energy.
However, the z-component of the angular momentum cannot be exactly determined for these states - it is
uncertain with respect to sign. Since ml is not exactly known for the orbitals of subset (3B), one cannot use
the

ml

in the orbital symbol. The orbital symbol is derived from the orbital expressions like in case of the

orbitals of the subset (2). The linear combination of the subset (3A)-orbitals with ml result in two orbitals
corresponding to cos|ml | and sin|ml | as the -parts, respectively. The rl from the radial part and the
and parts together can be simplified and exprssed in cartesian coordinate system to get the subscript. Thus,
the linear combinations of p1 orbitals give px and py orbitals, the linear combinations of d1 yield dxz and dyz
orbitals, the linear combinations of d2 result in dxy and dx2 y2 orbitals, and so on. Thus, from the orbitals
of the subset (3A) expressed earlier, we get the following orbitals of the subset (3B).
2px

= M reZr/2a0 sincos

(27)

2py

= M reZr/2a0 sinsin

(28)

= M r2 eZr/3a0 sin2cos

(29)

3dxz

3dyz

M r2 eZr/3a0 sin2sin

(30)

3dx2 y2

M r2 eZr/3a0 sin2 cos2

(31)

3dxy

M r2 eZr/3a0 sin2 sin2

(32)

To summarize, the characterization of hydrogenic orbitals can be quickly done from the orbital expressions
as they reflect the quantum numbers n, l and (in some cases) ml . The quantum numbers n and l appear in
the radial wavefunction. Consequently, the characterization of the sub-shell is possible just from the radial
wavefunction. The angular wavefunction describes the details about the quantum number l in the form of
the polynomial/function in reflecting the the orientation along or away from the z-axis. In case of pureml -orbitals, the z-component of the angular momentum is exactly obtained, whereas the linear combinations
of orbital-pairs corresponding to ml results in the pair of orbitals which are more expressive about the
orientations of the maximum probability density while loss of the accuracy in the z-component of the angular
momentum.
A question that would naturally pop up here, is, Which set of orbitals is the more correct one?. The
answer to this is, both the sets are correct. However only one of them may be used at a time. Which set of the
orbitals is to be used depends on what properties one is interested in. For example, while studying the effect
of external magnetic field on the atomic energy levels, the use of pure ml orbitals (equations (24, 25, 26)) is a
more natural choice than the px , py , etc. orbitals. However, while studying the effect of external electric field,
the use of the orientation-expressive orbitals is a more convenient choice.