Understanding the Hydrogenic orbital expressions

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

September 1, 2023

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 Schrödinger 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 Schrödinger 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). We’ll study both these parts and learn how to characterize the orbitals from the mathematical
expressions.

1 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

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following general form.  
n−l−1
X
Rn,l (r) = Nn,l rl  (−1)j cj rj  e−Zr/na0 (1)
j=0

In the above expression, Nn,l is the normalization constant. In principle, rl could have been absorbed in the
polynomial and we could have written the radial wavefunction as
 
n−1
X
Rn,l (r) = Nn,l  (−1)j−l cj rj  e−Zr/na0 (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. (To be more specific, each r in the above expressions should actually
be replaced by Zr/a0 . Of these, the a0 in the denominators of r ensure that the (unnormalized) wavefunctions
is dimensionless. However, since both Z and a0 are constants, they may as well be absorbed in the coefficients
and the normalization constants in the expression above. The normalization constant would have an additional
−3/2
a0 dependence that will ensure that the total probability is dimensionless. In the actual expressions expanded
for specific cases, we have used Zr/a0 in the polynomials because the the exact coefficients have accordingly,
been chosen. However, (Zr/a0 )l , we have used rl only with the understanding that the normalization constant
would appropriately absorb the (Z/a0 )l , because rl is just more convenient in order to appreciate the cartesian
forms useful for the orbital characterization).
The bracket contains the polynomial of degree n − l − 1 in r and must have the terms starting from r0
to rn−l−1 . The coefficients cj ’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 = N1,0 e−Zr/a0 (3)

R2,0 = N2,0 (2 − Zr/a0 ) e−Zr/2a0 (4)

R2,1 = N2,1 re−Zr/2a0 (5)

= N3,0 27 − 18(Zr/a0 ) + 2(Zr/a0 )2 e−Zr/3a0

R3,0 (6)

R3,1 = N3,1 r (6 − Zr/a0 ) e−Zr/3a0 (7)

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 R3,2 = N3,2 r2 e−Zr/3a0 (8)

= N4,0 192 − 144(Zr/a0 ) + 24(Zr/a0 )2 − (Zr/a0 )3 e−Zr/4a0

R4,0 (9)

= N4,1 r 80 − 20(Zr/a0 ) + (Zr/a0 )2 e−Zr/4a0

R4,1 (10)

R4,2 = N4,2 r2 (12 − Zr/a0 ) e−Zr/4a0 (11)

R4,3 = N4,3 r3 e−Zr/4a0 (12)

The following points are to be noted and understood in the above expressions.

ˆ The equations (3,4, 6 and 9) correspond to s-type orbitals. Since, l = 0 for these orbitals, the rl term
doesn’t appear in these expressions. The equations (5,7 and 10) correspond to p-type orbitals (charac-
terised 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).

ˆ The orbitals of the subshells, 1s, 2p, 3d and 4f will have no radial nodes as n − l − 1 = 0 for these orbitals.
Therefore, no polynomial in r is found in the equations (3, 5, 8 and 12). The equations (4, 7 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).

ˆ 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.

ˆ 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 e−Zr/na0 are consistent with the degree (n − l − 1) of
the respective polynomials.

2 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 (θ, ϕ) and
are expressible as product of pure functions of θ and ϕ, respectively.

Yl,ml (θ, ϕ) = Θl,|ml | (θ)Φml (ϕ) (13)

The functions Φml (ϕ) is obtained on solving the azimuthal wave-equation, which is obtained by separating
the ϕ-dependent terms from the rest of the Schrödinger equation. The azimuthal wave-equation is identical

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to the Schrödinger equation for particle on a ring and the eigenfunctions are 1
(2π)1/2
e±i|ml |ϕ , where ml is an
integer. The lower and upper bounds to ml are actually imposed upon solving the θ-dependent part (polar
wave-equation) of the Schrödinger 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 cosθ and
sinθ. First few polar wavefunctions are presented here.

Θ0,0 = P0,0

Θ1,0 = P1,0 cosθ

Θ1,±1 = P1,±1 sinθ

Θ2,0 = P2,0 (3cos2 θ − 1)

Θ2,±1 = P2,±1 sin2θ

Θ2,±2 = P2,±2 sin2 θ

Θ3,0 = P3,0 (5cos3 θ − 3cosθ)

Θ3,±1 = P3,±1 sinθ(5cos2 θ − 1)

Θ3,±2 = P3,±2 sin2 θcosθ

Θ3,±2 = P3,±3 sin3 θ (14)

The Pl,ml ’s in the above expressions are the normalization constants.

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 ϕ and the
polar wavefunction is a pure polynomial in cosθ. For all other orbitals, the polar wavefunction is multipled by
an azimuthal (ϕ-dependent) wavefunction. The polar wavefunction for such orbitals is defined as a polynomial
in cosθ of rank (l − |ml |) times as sin|ml | θ. The polynomial in cosθ is essentially even or odd polynomial
corresponding to the even or odd value of l − |ml . The solution of the polar wave-equation is somewhat involved
and as far as the General Chemistry course is concerned, we won’t worry about how-to-solve-it. We will rather
only study how to use those solutions.
Please note that ml = 0 states correspond to the orientation of the angular momentum vector along xy-plane
and the probability densities of the corresponding states would be dominated along z-axis which is obvious from
the polynomials of cosθ. sinθ is zero along z-axis and is maximum along xy-plane. The increase in ml makes
the density gradually displace from z-directions towards the xy-plane. This idea will be more clear when we
combine these expressions with relevant Φml (ϕ) and the radial expressions to get the hydrogenic orbitals.

3 The total wavefunctions (Hydrogenic orbitals)

Based on the form of the angular wavefunctions, we divide the orbitals into three sub-sets:

(1) Orbitals with l = 0.

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(2) Orbitals with l > 0 and ml =0.

(3) Orbitals with l > 0 and ml ̸= 0.

The orbitals belonging to the subset (1) are the s-orbitals. Being θ-independent as well as ϕ-independent
(since, Y0,0 (θ, ϕ) = (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.

Ψ1s = M1,0,0 e−Zr/a0 (15)

Ψ2s = M2,0,0 (2 − Zr/a0 ) e−Zr/2a0 (16)

2
e−Zr/3a0


Ψ3s = M3,0,0 27 − 18(Zr/a0 ) + 2(Zr/a0 ) (17)

192 − 144(Zr/a0 ) + 24(Zr/a0 )2 − (Zr/a0 )3 e−Zr/4a0

Ψ4s = M4,0,0 (18)

In the above orbital expressions (and the orbital expressions hereafter), Mn,l,ml are the normalization constants,
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.

Ψ2pz or Ψ2p0 = M2,1,0 re−Zr/2a0 cosθ (19)

Ψ3pz or Ψ3p0 = M3,1,0 r (6 − Zr/a0 ) e−Zr/3a0 cosθ (20)

M4,1,0 r 80 − 20(Zr/a0 ) + (Zr/a0 )2 e−Zr/4a0 cosθ

Ψ4pz or Ψ4p0 = (21)

Ψ3dz2 or Ψ3d0 = M3,2,0 r2 e−Zr/3a0 (3cos2 θ − 1) (22)

Ψ4dz2 or Ψ4d0 = M4,2,0 r2 (12 − Zr/a0 ) e−Zr/4a0 (3cos2 θ − 1) (23)

Ψ4fz3 or Ψ4f0 = M4,3,0 r3 e−Zr/4a0 (5cos3 θ − 3cosθ) (24)

In the above expressions, note the rl factor from the radial part and the cosl θ term in the angular part. The
rl cosl θ equals (rcosθ)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 cosθ may be
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 ̸= 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).

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 The orbitals corresponding to subset (3A) have exactly known ml are characterized by eiml ϕ . 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 , 2p−1 , 3d−2 , 4f+3 , etc.

Ψ2p±1 = M2,1,±1 re−Zr/2a0 sinθe±iϕ (25)

Ψ3d±1 = M3,2,±1 r2 e−Zr/3a0 sin2θe±iϕ (26)

Ψ3d±2 = M3,2,±2 r2 e−Zr/3a0 sin2 θe±2iϕ (27)

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 ̸= 0) and obtain the new orbital-pairs for which the
orientation(s) of the maximum probability density can be identified. For convenience, we will call these linearly
combined orbitals as orientation-instructive orbitals.
The orientation-instructive orbitals constitute the subset (3B) and are, the eigen-functions of the Hamiltonian
operator as well as of the angular momentum squared operator - but not of the z-component of the angular
momentum. Therefore, these correspond to the electronic states with exactly known energy as well as exactly
known magnitude of orbital angular momentum, but the z-component is not exactly known as it is uncertain in
terms of sign. It may, however, be noted that, if the operator corresponding to the square of the z-component
of the angular momentum is concerned, then these orbitals are still the eigenfunctions with the eigenvalues as
m2l h̄2 . Thus, m2l is perfectly known for these orbitals and, consequently, the ml is uncertain only in terms of sign.
Since ml is not exactly known for the orbitals of subset (3B), it is not written in the orbital symbols. Rather, the
rl part of the radial function combined with the angular part is converted to the corresponding cartesian forms
that are useful in characterizing the orbitals. The linear combination of the subset (3A)-orbitals with ±ml result
in two orbitals corresponding to cos|ml |ϕ and sin|ml |ϕ as the Φ-parts, respectively. These, combined with the
rl from the radial part yield the cartesian forms that used as the subscripts of the corresponding orbitals. For
example, the linear combinations of p±1 orbitals give px and py orbitals, the linear combinations of d±1 yield
dxz and dyz orbitals, the linear combinations of d±2 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).

Ψ2px = M2,1,±1 re−Zr/2a0 sinθcosϕ (28)

Ψ2py = M2,1,±1 re−Zr/2a0 sinθsinϕ (29)

Ψ3dxz = M3,2,±1 r2 e−Zr/3a0 sin2θcosϕ (30)

Ψ3dyz = M3,2,±1 r2 e−Zr/3a0 sin2θsinϕ (31)

Ψ3dx2 −y2 = M3,2,±2 r2 e−Zr/3a0 sin2 θcos2ϕ (32)

Ψ3dxy = M3,2,±2 r2 e−Zr/3a0 sin2 θsin2ϕ (33)

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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 θ reflecting the the orientation along or away from the z-axis. In case of pure-ml -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. Rather, these orbitals are
obtained because we intended to determine magnitude as well as orientation in addition to energy. Which set
of the orbitals is to be used depends on what properties one is interested in. For example, while studying the
Zeeman effect (splitting of atomic spectral lines upon application of external magnetic field), the use of pure ml
orbitals (equations (25, 26, 27)) is a more natural choice than the px , py , etc. orbitals. However, the Stark effect
(spectral line splitting due to strong external electric field) is better studied using the orientation-instructive
orbitals as a more convenient choice.