1

HYDROGENIC ATOMS

Dr. M. Monirul Islam

Professor of Chemistry
University of Rajshahi
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HYDROGEN ATOM
Central force problem:
 The interacting force between two
particles depend on only the separation
𝑚𝑒 𝑟 between them.
 Independent on the orientation i.e. and
 Potential energy of electron due to
𝑚 nuclear charge

 Since depends only on the , hydrogen

atom (hydrogen-like) can be treated as
central force problems

 Further, hydrogen atom consists of one electron and nucleus, so it

is a two-body problem.
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HYDROGEN ATOM
 From the result of reducing two-body problem to one-body
problem, we can write the kinetic energy operator for H

Where, , , R = coordinate of center of mass, and r is relative

coordinates of electron with respect to nucleus.
 Hamiltonian operator for H atom

 Schrodinger equation for H atom

Translational electrical This part depends only on

motion motion coordinates of electron
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HYDROGEN ATOM
Separation of translational and electrical motion
 Since translation motion does not interfere the electronic part,
total wavefunction, can be written as

 Double differentiating of with respect to and gives

 Inserting above derivatives in SE for H gives

 Dividing both sides by results

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HYDROGEN ATOM
Separation of translational and electrical motion
 LHS depends on only the center of mass coordinates whereas
RHS depends on the relative coordinates, , hence both sides
must equal to the same constant, say .
 Thus we obtain two separate equations:

(1)

(2)
 Rearranging eq. (2) we get

 Eq. (1) leads

(3)

(4)
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HYDROGEN ATOM
Separation of translational and electrical motion
 Eq. (4) represents the SE for translational motion of
hypothetical mass . This equation is similar to SE of free particle
confined in a box.
 In practical , hence eq. (4) mainly reveals the SE of nucleus.

 The eq. (3), which contains the potential energy of interaction

between electron and nucleus, is actually SE for internal motion
of nucleus and electron.
 In practical, leads , hence eq. (3) becomes

 In eq. (5) represents the energy of electron in the atom. (5)

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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
 In spherical coordinate, Laplacian operator can be written as,

[ ]
2

( )
2 𝜕 2𝜕 1 2 1 𝜕 𝜕 1 𝜕
2
𝛻 = + + 2 Λ where, Λ =2
sin 𝜃 +
𝜕𝑟
2
𝑟 𝜕𝑟 𝑟 sin 𝜃 𝜕 𝜃 𝜕 𝜃 sin 2 𝜃 𝜕 𝜙 2
 SE in spherical coordinate

(5)
 Note that from particle on sphere or 3D rigid rotator, we have learnt
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
 The eq. (5) depends on three variables (). To solve it, it is necessary to
separate in independent variable. If it is assumed that and does not
interfere each other, then can be written as,

(6)

 From relation (6) we have,

 Using these relations in eq. (5) we obtain

(7)
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
 Multiplying both sides of eq. (7) by results

 LSH of eq. (8) depends on and , while RHS on only. This equality is
(8)
only hold if both sides is equal to the same constant, say , which gives
two equations,

(9)

………….(10)
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)

 Dividing eq. (10) by and rearranging dependent terms on LHS and

dependent on RHS,

(11)
 Again LSH of eq. (11) depends on , while RHS on only. This equality is
only hold if both sides is equal to the same constant, say , which gives
two equations,

(12)

(13)
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
 For the sake of convenience, we rewrite eq. (9), (12) and (13) together

(14)

(15)

 Solutions of eq. (14) and (15) have been shown in particle on sphere or
3D rigid rotator. The combined solution is spherical harmonics . (16)
 The eq. (16) is called radial equation and is new. Now we try to solve
this equation.
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
equation:
 The eq. (14) is similar to particle on ring or 2D rotator. Its normalized
solution is

equation:
 The eq. (15) is similar to the part of particle on sphere or 3D rotator.
Its solution is associated Legendre polynomial

Where N is normalization constant and is given by

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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
Spherical Harmonics
The product of and is denoted by . For a given values of
and ,the normalized wave functions, are called the
spherical harmonics and given by
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
Spherical Harmonics
Example: Evaluate
Soln: If then
For and
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
Spherical Harmonics
The for some and are given in Table1.

(29)
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BACKGROUND 1
Laguerre Polynomial:
Let
Differentiating gives

e.g.,
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BACKGROUND 1
Associated Laguerre Polynomial:
 Pth derivative of Laguerre polynomialis known as Associated
Laguerre polynomial, which is the solution of following
differential equation, called associated Laguerre differential
equation.

 The associated Laguerre polynomial is of degree and order ,

where . Replacing by , by and by , where Or,
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
The equation:
(17)
 Note that third term in bracket adds an additional terms to the
potential energy. Previously, it was shown that . So it is obvious
that third term comes from the angular momentum and counts the
centrifugal force that acts against the coulombic force. Thus,
effective potential energy is given by

𝑙> 0

Fig. The effective potential experienced by an electron

in a hydrogen atom. When l > 0 centrifugal contribution

0
prevents the close approach of the electron to the

𝑙=
nucleus, as it increases more rapidly (as ) than the
Coulomb attraction (which varies as ). Radius,
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
The equation:
 To simplify eq. (17), put dimensionless variable, , where is constant
and its dimension is reciprocal to

 Now eq. (17) becomes

(18)
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
The equation:
 For convenient, is chosen so that first term in bracket becomes
and coefficient of is defined by n, i.e.,

 Now eq. (18) becomes

 For large , becomes infinitesimal and eq. (19) becomes

(19)

(20)
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
The equation:
 Solution of eq. (20)

 The positive exponent makes infinite and is not acceptable. The

acceptable function is

 For small , then eq. (19) reduces to

(21)
 Let assume the solution of eq. (21) is
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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
The equation:
 Inserting this function in eq. (21) gives

 Function may be

 The latter solution approaches to infinity as increases and is not

acceptable. The acceptable solution is

 For intermediate values of , the solution of eq. (19) is given by (22)

Where is a polynomial of power series in . is to be determined.

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HYDROGEN ATOM
Solution of SE for H (hydrogenic atom)
The equation:
 Inserting eq. (22) in eq. (19) gives

(23)
 The solution of eq. (23) is the associated Laguerre polynomial (see
background 1), which is given as

 The degree of polynomial is and order with the condition or .

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HYDROGEN ATOM
Nature of and
 From it is concluded that
 The minimum degree is zero, i.e.,
 Since lowest value of is 1, above condition says that the lowest
value of is zero.
 Further, the degrees of polynomial are integers, hence acceptable
values of and are integers.
 Therefore, acceptable values of are 1, 2, 3, and are 0, 1,2,
 For , exists
 However, for or , does not exist.
 For example, let and
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HYDROGEN ATOM
Atomic Units (au)
 The units used for macroscopic scale are not convenient in
quantum mechanics. Further, quantum mechanical equations in
terms of fundamental constants are very cumbersome to handle.
 The units that are designed to simplify the form of the
fundamental equations of quantum mechanics by eliminating from
them fundamental constants are atomic unit (au).
 The advantage of atomic units is that if all calculations are
directly expressed in such units, the results do not vary with any
revision of the numerical values of the fundamental constants.
 If we introduce a set of units such that and

,
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HYDROGEN ATOM
Some fundamental constants in atomic units (au)
Quantity Atomic Unit SI equivalent
Mass (electron mass) kg
Charge (electronic charge) C
Angular
momentum Js
Permitivity
Length (bohr) (Bohr radius) m

Energy (hartree) (twice the ionization energy of atomic J

hydrogen)

Time (period of an electron in the first Bohr orbit) s

Speed (speed of an electron in the first Bohr orbit)

Electric potential (potential energy of an electron in the first Bohr V

orbit)

Magnetic dipole (twice a Bohr magneton)

moment
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HYDROGEN ATOM
Ex. One hartree, the unit of energy in atomic units, is given by
Express one hartree in units of joules (J), kilojoules per mole (), wave numbers ()
and electron volts (.
Solution: To find one expressed in joules, we substitute the SI values of and
into the above equation.

If we multiply this result by Avogadro’s number, we obtain

To express one in wave numbers (, we use the equation

Lastly, to express one in terms of electron volts, we use the conversion factor
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HYDROGEN ATOM
Radial wavefunctions
 The radial wavefunction is written as

 In terms of
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HYDROGEN ATOM
Some examples of radial wavefunctions
 For and
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HYDROGEN ATOM
Some examples of radial wavefunctions
 For and
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HYDROGEN ATOM
Some examples of radial wavefunctions
 For and
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HYDROGEN ATOM
Graphical representations of radial wavefunctions
2.0 0.4
0.6
1.5
1s 0.4 2s 3s
Rn0(r)

Rn0(r)

Rn0(r)
0.2
1.0
0.2
0.5
0.0 0.0
0.0
1 3 5 2 6 10 14 2 6 10 14
r/au r/au r/au
0.10
0.15 0.04
2p 0.05 3p 3d
0.10
Rnl(r)

Rnl(r)

Rnl(r)
0.02
0.05 0.00
0.00 0.00
-0.05
2 6 10 14 2 6 10 14 2 6 10 14
r/au r/au r/au
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HYDROGEN ATOM
Graphical representations of radial wavefunctions

 The functions with are non-zero (and finite) at ,

whereas all the functions with are zero at .
 Each radial wavefunction has nodes (the zero
amplitude at for functions with are not nodes).
 The locations of these nodes are found by
determining where the polynomial in the
associated Laguerre function is equal to zero.
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HYDROGEN ATOM
Complete wave functions or atomic orbitals of hydrogenic atoms
 It is product of , and dependent wavefunctions

where , and are the three quantum number used to

characterize the wave function.
 For example, for , , , the wave function is

 In atomic unit,

 For hydrogen atom,

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HYDROGEN ATOM
Complete wave functions or atomic orbitals of hydrogenic atoms
 The wave functions for hydrogenic atoms are also called atomic
orbitals.
 Prior to the development of quantum mechanics, the atomic orbitals
are denoted as for respectively. The letters being preceded by
numbers representing principle quantum numbers. Thus we have , ,
atomic orbitals corresponding to , , respectively
 Since the energy of hydrogenic atoms depends only on and
independent of and , orbitals having same and different and are
degenerate. Thus we have the following hierarchy of energy states
of hydrogenic atoms:

 Wherein the degenerate states are bracketed. To specify magnetic

quantum numbers, we may add the subscripts as follows:
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HYDROGEN ATOM
Energy (Eigenvalues) of hydrogenic atoms
 To simplify the r-equation, 2 constants, and were introduced

 Eliminating from eq. (1) and (1)

(2) (2)

 Nucleus mass of H atom leads

 Eigenvalue of H atom in ground state (au)

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HYDROGEN ATOM
Energy (Eigenvalues) of hydrogenic atoms
 To simplify the r-equation, 2 constants, and were introduced

 Eliminating from eq. (1) and (1)

(2) (2)

 Nucleus mass of H atom leads

 Eigenvalue of H atom in ground state (au)

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HYDROGEN ATOM
The degeneracy of Hydrogenic atoms
 The energies of hydrogenic orbitals depend only on the
principal quantum number but not on .
 Hence the total energy is independent of , and all orbitals
with the same value of have the same energy.
 Because the permissible values of are , and for each value
of there are orbitals, the degeneracy of a level with
quantum number is
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HYDROGEN ATOM
Loss of degeneracy of AO in magnetic field
 The electron rotating round the nucleus has also magnetic moment
() vector colinear with the vector and is proportional to it.

 interacts with magnetic filed say H applied in the direction of z-

axis, the interaction energy is

𝜓 211
𝜓 21, −1
H
𝜓 200 𝜓 210 𝜓 211 𝜓 200 𝜓 210

𝜓 21, −1
Degenerate AOs
corresponding to n=2 Non-degenerate AOs
corresponding to n=2
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HYDROGEN ATOM
Probability density,
 represents the charge per unit volume (electron density

1s 2s 3s
y2(r)

y2(r)

y2(r)
r/au r/au r/au
 The plot show that electron density is maximum at in case of
and decays exponentially.
 It contradicts to Bohr atomic structure. Since is the
probability per volume and not actual probability of finding
electron at a point.
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HYDROGEN ATOM
Radial probability density,
 The quantity is the radial probability density that signifies the
probability density for the electron to be at a point located the
distance from the nucleus.

𝑟 ( 𝑎 0) 𝑟 ( 𝑎 0) 𝑟 ( 𝑎 0)
 Radial probability density is maximum at in case of and decays
exponentially.
 Because with has no Laguerre polynomial which would increase
rather the exponential part dominates.
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HYDROGEN ATOM
The radial distribution function (RDF)
 The actual probability of finding electron at any point is given by ,
where
 It is sometimes crucial to know the total probability of finding
the electron at a given radius regardless of the direction.
 A radial distribution function, is obtained by integrating over all
angles and but not over .

The radial distribution function

gives the probability density for
 It is also called radial probability density function an electron to be found
anywhere on the surface of a
 More generally, for any wavefunction (an s-orbital), is equivalent
sphere locatedto .
a distance from
the nucleus.
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HYDROGEN ATOM
Some RDFs

 is maximum at , whereas for , why?

─ in makes its zero at but in exponent of makes maximum at .
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HYDROGEN ATOM
Applications of RDFs
(a) Radial probability of finding electron in spherical shell
It is the probability of finding the electron
within the spherical shell enclosed between
a sphere of radius and a sphere of radius
from the nucleus.
𝑑𝑟
2
𝑅𝑛𝑙 (𝑟 ) 𝑟
2
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HYDROGEN ATOM
Applications of RDFs
(2) Points of maximum probability
 passes through some maximum points due to compromising
effect of and exponential part of radial wave functions
 The maximum point can be determined by differentiating with
respect to and setting to zero.
 For example, in au

For H atom , , which is the radius of first Bohr orbit.

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HYDROGEN ATOM
Applications of RDFs
(2) Points of maximum probability
 passes through some maximum points due to compromising
effect of and exponential part of radial wave functions
 The maximum point can be determined by differentiating with
respect to and setting to zero.
 For example, in au

For H atom , , which is the radius of first Bohr orbit.

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HYDROGEN ATOM
Average distance of the electron from nucleus
 The average distance, of the electron from the
nucleus is a fundamental properties.
 For hydrogen in the 1s state,
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ANGULAR MOMENTUM
The classical expression of angular
momentum,

Writing
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ANGULAR MOMENTUM
Angular momentum operators
 The commutation relations among
the three components of angular
momentum operators

[^
𝐿𝑥 , ^ ^
𝐿 𝑦 ]=𝑖ℏ 𝐿 𝑧
are not commute
and they can not
[^
𝐿 ,^
𝑦 𝐿 ]=𝑖ℏ 𝐿
𝑧
^
𝑥
be determined
simultaneously
[^
𝐿𝑧 , ^
𝐿𝑥 ]=𝑖 ℏ ^
𝐿𝑦
 The commutation relations between angular momentum
operator and its components ()

[^
𝐿 ,^
2
𝐿𝑥 ]=0 ^ 2 ^
[ 𝐿 , 𝐿𝑦 ]=0 [^
𝐿 ,^
2
𝐿𝑧 ]=0
 and its components are commute indicating that
and its one of the components can be determined
simultaneously
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ANGULAR MOMENTUM
Angular momentum operators

Converting to polar coordinates,

 51

ANGULAR MOMENTUM
In case of particle on ring
Applying and to

Note that,
 is the wavefunction of both and .
 and can be determined simultaneously from .
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ANGULAR MOMENTUM
However, the eigenfunction of in real form is not
eigenfunction of

Note that,
 The eigenvalue of is
where
If ; is positive,
If ; is negative.
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ANGULAR MOMENTUM
In case of particle on sphere
Applying , and to
 54

ANGULAR MOMENTUM
Representation of Angular Momentum
Z

ℏ
1)⋅
𝐿𝑧=𝑚𝑙 ℏ

√ 𝑙 (𝑙 +

𝐿=

Orientation of L vector with z-axis

𝑚𝑙 𝑚𝑙 ℏ 𝑚𝑙
cos 𝜃= = =¿ ¿
𝐿 ℏ √ 𝑙(𝑙+1) √ 𝑙(𝑙 +1)
 For given , has only values
 For given , has only orientations with z-
axis
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HYDROGEN ATOM
Significance of the quantum numbers , and

 State of an electron can be represented by from which the

following three important quantities can be extracted:

where is principal quantum number

is angular momentum (azimuthal) quantum number

is magnetic quantum number

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HYDROGEN ATOM
Significance of the quantum numbers , and

 With increase in , increases. Also, size of atom is directly

proportion to n2. thus reflects size and energy of atoms.

 determines the angular momentum of electron. Further, is

equal to the number of nodes presence in AO. Nodes
determines the shape of AO. Thus, reflects the angular
momentum of electron in orbital and shape of AO.

 arises from the fact that when an atom is placed in a

magnetic field, the degenerate states split up into different
states, each state is characterized by its value (Zeeman
effect). The orientation of orbital with external magnetic
field determines magnetic orbital quantum number.
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HYDROGEN ATOM
Atomic Orbitals
 One-electron wavefunctions in atoms are called atomic
orbitals. It is described by wavefunction, or .
 Orbitals with are called -orbitals respectively.
 An electron that occupies an s-orbital is called an s-electron,
and similarly for electrons that occupy other types of
orbitals.
 of AOs always real. with are real and can be drawn real
picture. with are complex due to the presence of and
cannot be drawn real picture.
 It is usual to depict the real and imaginary components.
 Real component,
 Imaginary component,
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HYDROGEN ATOM
Real versus Complex atomic orbitals
Topics Real AOs Complex AOs
Eigenvalues Real and Complex AOs have the Real and Complex AOs
same eigenvalues have the same eigenvalues
Formation AOs with are real. Linear AOs with are always
combination of AOs with and complex AOs
gives real AOs.
Magnetic Real AOs generated from linear Complex AOs retain the
quantum number combination lose the significance of
() significance of
Graphical Can be drawn real picture Cannot be drawn real
representation picture
Wavefunction Wavefunctions of and meaning Wavefunctions of , and
that and can be determined meaning that , and can be
simultaneously through an determined simultaneously
experiment. through an experiment.
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HYDROGEN ATOM
s-orbitals
( )
3/ 2
1 𝑍 −𝜌
 s-orbital does not depend
𝜓 1 𝑠= 𝑒 Where
√ 𝜋 𝑎0
on and i.e., spherical
𝜌

√ ( )
harmonics. 1 𝑍 3/2 −
𝜓 2𝑠= ( 2− 𝜌) 𝑒 2
 Shape of s-orbital is 4 2 𝜋 𝑎0
independent of and . 𝜌

√ ( )
3 /2
2 𝑍 −
 Only depend on . s-orbital 𝜓 3 𝑠 = ( 27 −18 𝜌 + 2 𝜌 ) 𝑒 3
2

is spherically symmetric. 81 3 𝜋 𝑎0
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HYDROGEN ATOM
s-orbitals
 For s-orbital, , orbital angular momentum,

 That means s-electron has no rotational motion and therefore

cannot be moving around the nucleus.
 According to classical mechanics, elections with (zero ) would
plunge into nucleus due to nuclear attraction. How can it be
explained by QM?
 has maximum amplitude at (at nucleus) that means the s-
electrons are captured by nucleus- collapse atom!!!
 61

x
y
62
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64
65
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HYDROGEN ATOM
Graphical Representation of Spherical Harmonics:

𝑌 0, 0

𝑌 1 ,1 +𝑌 1 ,−1 →𝑌 1+ ¿¿ 𝑌 1 ,1 − 𝑌 1, −1 →𝑌 1 − 𝑌 1 ,0
 67

ROTATIONAL MOTION
Graphical Representation of Spherical Harmonics:

𝑌 2 ,0 𝑌 2 ,1 +𝑌 2 ,− 1 → 𝑌 2+¿ ¿ 𝑌 2 ,1 −𝑌 2 ,−1 → 𝑌 2 −

𝑌 2 ,2 +𝑌 2 , −2 → 𝑌 2+¿ ¿ 𝑌 2 ,2 −𝑌 2 ,− 2 → 𝑌 2−
 68

HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Presentation of Atomic orbitals
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HYDROGEN ATOM
Angular probability functions
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HYDROGEN ATOM
Angular probability functions
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HYDROGEN ATOM
Angular probability functions
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HYDROGEN ATOM
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HYDROGEN ATOM
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HYDROGEN ATOM
Probabilities and the radial distribution function
 The probability of finding an electron in a volume element at a
point specified by the spherical polar coordinates () when the
state of the electron is described by the wavefunction is given
by

 Although the wavefunction gives the probability of finding an

electron at a specified location, it is sometimes more helpful to
know the probability of finding the particle at a given radius
regardless of the direction. This probability is obtained by
integration over the volume contained between two concentric
spheres of radii and

The radial distribution function gives the probability

that an electron will be found anywhere between two
concentric spheres with radii that differ by dr.