Lecture 4: Hydrogen Atom

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What have we learnt?
Formulate a correct Hamiltonian
(energy) Operator H

Solve TISE H=E 

by separation of variables and
intelligent trial wavefunction

Impose boundary conditions for

eigenfunctions and obtain
Quantum numbers

Eigenstates or Wavefunctions:
Should be “well behaved” -
Normalization of Wavefunction

Probabilities and Expectation Values

Recapitulation: Basics of Quantum Mechanics

• Schrödinger equation: Classical wave equation for

de Broglie waves

• Eigenvalue equation: Ây = ay

• Expectation values:
ò y * Ây dt
ò y * y dt
• Boundary conditions: Quantization
 Recapitulation: Free Particle

2
2
  ( x )  E  ( x ) y(x) = Asinkx + Bcoskx
2m x 2

2 2
k2 2mE
k  ( x )  E  ( x )
2
 E  k
2m 2m

No Quantization, all energies are allowed

 Recapitulation: Particle in 1-D Square-Well
Potential

ì ¥ x <0
ï
V (x) = í 0 0£ x £ L
ï ¥ x>L y(x) = Asinkx + Bcoskx
î
Boundary Conditions:
y (x) = 0 Þ y(x) = Asinkx ∵ cos0 = 1

y (L) = 0 Þ AsinkL = 0 Þ sinkL = 0 kL = np n=1,2,3,4...

np Normalization: 2 np
y (x) = Asin x y (x) = sin x
L L L
Recapitulation: Particle in 2-D Square-Well
Potential
V=0
y (x,y) = y (x)× y (y)
Ly
2 np 2 np
= sin x× sin y
L L L L
2 np np Lx
= sin x × sin y
L L L Square Box
 L x = Ly = L

En ,n
= En + En
x y x y

nx2h2 ny2h2 Separation of variables

= +
8mL 8mL2 2

=
h2
8mL 2
n 2
x
+ n(
y
2
) nx ,ny = 1,2,3,4...
Recapitulation: Particle in 2-D Rectangular-Well
Potential
y (x,y) = y (x)× y (y) V=0
2 np 2 np Ly
= sin x× sin y
Lx Lx Ly Ly
2 np np Lx
= sin x × sin y
Lx Ly Lx Ly

En ,ny
= En + En
x x y

nh 2 2
ny2h2
= x
2
+
8mL x
8mL2y
æ n2 n2 ö
2
h ç x y ÷
= + nx ,ny = 1,2,3,4...
8m çè Lx Ly ÷ø
2 2
Hydrogen Atom

(xe,ye,ze) Two particle central-force problem

Completely solvable – a rare example!

(xN,yN,zN)

 2
 2
 2
 2
 2
 2
2N  2  2  2 2e  2  2  2
x N yN z N xe ye ze
Hydrogen Atom

Schrödinger Equation

YTotal = Y(x N ,yN ,z N ,xe ,ye ,ze )

 Hydrogen Atom: Relative Frame of Reference

Separation of Ĥ into Center of Mass and Internal co-ordinates

me xe  m N xn
X
z me(xe,ye,ze) x = xe - x N me  m N
re - reN
y = ye - yN me ye  mN yn
CM M Y
R N
me  m N
r (xN,yN,zN)
N
z = ze - z N
y me ze  m N zn
Z
r = reN = re - rN me  m N
x rN = (x 2
+y +z
2 2
) me re  m N rN
(x )
N N N
= 2
+y +z
2 2 R
me  m N
re = ( xe2 + ye2 + ze2 )
Hydrogen Atom: Relative Frame of Reference

Checkout Appendix-1
 Hydrogen Atom: Separation to Relative Frame

Hydrogen atom has two particles the nucleus and

electron with co-ordinates xN,yN,zN and xe,ye,ze

The potential energy between the two is function of

Appendix-1

relative co-ordinates x=xe-xN, y=ye-yN, z=ze-zN

r = ix + jy + kz z me(xe,ye,ze)
re - reN
x = xe - x N ,y = ye - yN ,z = ze - z N R
CM M
N
rN (xN,yN,zN)
y
R = iX + jY + kZ x
me xe + mN xn me ye + mN yn me ze + mN zn
X= ,Y = ,Z=
me + mN me + mN me + mN
 Hydrogen Atom: Separation to Relative Frame

mere + mN rN
R=
me + mN
Appendix-1

r = reN = re - rN

mN z me(xe,ye,ze)
re = R - r re - reN
me + mN CM M
R N

me rN (xN,yN,zN)
rN = R - r y
me + mN
x
 Hydrogen Atom: Separation to Relative Frame
Appendix-1
 Hydrogen Atom: Separation to Relative Frame
Appendix-1

In the above equation the first term represent the

kinetic energy of the center of mass (CM) motion and
second term represents the kinetic energy of the relative
motion of electron and
Hydrogen Atom: Separation of CM motion

YTotal = c N × ye ETotal = EN + Ee

Free particle!
Kinetic energy of the atom

?
Hydrogen Atom: Electronic Hamiltonian

ye Þ ye (x,y,z)

v
v
 Hydrogen Atom: Electronic Hamiltonian

ye Þ ye (x,y,z)

Not possible to separate out into three different co-ordinates.

Need a new co-ordinate system
Spherical Polar Co-ordinates

z = r cosq
x = r sinq cos f
y = r sinq sin f

r:0 to ∞
: 0 to 
: 0 to 2

d  dx  dy  dz  r 2  dr  sin  d  d
Laplacian in Spherical Coordinates
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
 Laplacian in Spherical Coordinates
Appendix-2
Laplacian in Spherical Coordinates
Hamiltonian in Spherical Coordinates
Schrodinger equation for the electronic part in
Spherical Polar Co-ordinates

and bring all the terms to the LHS

Separation of variables

ye (r,q ,f ) Þ R (r ) × Q(q )×F(f )

ye Þ R×Q× F
Separation of variables

Upon differentiation
Separation of variables

1
Multiply with
R

1   2 R  1 1     1 1  2
 r    sin   
R r  r   sin       sin 2   2
2  rQZe 2 2 r 2
 2
 2 Ee  0
Separation of variables

Rearrange

Radial Angular

=
A constant
Separation of variables

Radial equation

Angular equation
 Separation of variables

Radial equation

Angular equation

Multiply with sin2  and rearrange

sin     1 2
 sin    sin   
2

       2

sinq ¶ æ ¶Q ö 1 ¶2F
ç sinq ÷ + b sin q = m = -m
2 2 2

Q ¶q è ¶q ø F ¶f 2
 Separation of variables

sinq ¶ æ ¶Q ö
ç sinq ÷ + b sin q = m
2 2

Q ¶q è ¶q ø

1 ¶2F
= -m 2

F ¶f 2

The three variables r,  and  are separated

 Solution to  part

1 ¶2F(f ) ¶2F(f )
+ m 2
=0 = -m 2
F(f )
F(f ) ¶f 2
¶f 2

¶F
Trial solution: ( )  Ae  im = ±imF
¶f

Wavefunction has to be continuous

‘’ ranges from 0 to 2  (  2 )  ( )

Periodic Boundary Condition

 Solution to  part

Þ F(f +2p ) = F(f )

Ameim(f +2p ) = Ameim(f ) and A-me-im(f +2 p ) = A-me-im(f )

eim(2p ) = 1 and e-im(2 p ) = 1

cos (2m) + i sin (2m) = 1

z
• True only if m=0, 1, 2, 3, 4,….

• What kind of information does  contain?

x
Change in : Circular motion in xy plane

z – component of angular momentum?

y
Angular momentum: from classical to quantum
picture

Is  an eigenfunction?
 Moment of truth

( )  Ae  im

z-component of angular momentum

m: Magnetic Quantum Number

“Space Quantization”
 Solution to  part

Þ F(f +2p ) = F(f )

Ameim(f +2p ) = Ameim(f ) and A-me-im(f +2 p ) = A-me-im(f )

eim(2p ) = 1 and e-im(2 p ) = 1

cos (2m) + i sin (2m) = 1

•True only if m=0, 1, 2, 3, 4,….

•m is the “magnetic quantum” number
•m is restricted by another quantum number (orbital Angular
momentum), l, such that |m|<l

sinq ¶ æ ¶Q ö 1 ¶2F
ç sinq ÷ + b sin q = m = -m
2 2 2

Q ¶q è ¶q ø F ¶f 2
 The  and the R part

Solve to get R(r)

1 ¶ æ ¶Q(q ) ö m2
ç sinq ÷ - 2 Q(q )+ bQ(q ) = 0
sinq ¶q è ¶q ø sin q

Solve to get ()

Need serious mathematical skill to solve these two equations.

We only look at solutions
 The  part

1 ¶ æ ¶Q(q ) ö m2
ç sinq ÷ - 2 Q(q )+ bQ(q ) = 0
sinq ¶q è ¶q ø sin q
Solution to () :
m l+m
(-1) m d
Pl m (cosq ) = l (1 - cos2 q ) 2 l+m (cos2 q -1)l
2 l! dx
l=0,1,2,3…
(l - m)! m
Pl -m (cosq ) = (-1)m Pl (cosq ) with b = l(l +1)
(l + m)!

Pl m (cos ):Associated Legendre Polynomials

New quantum number ‘l’ : orbital / Azimuthal quantum number
Restriction on m≤l
is due to this equation
The angular (·) part

The angular part of the solution

Yl m ( , )  ( )  ( ) are called spherical harmonics

(2l +1) (l - m)! m

Yl m (q ,f ) = Pl (cosq )eimf
4p (l + m)!

l=0,1,2,3…
m=0, ±1, ±2, ±3… and |m|≤l
 The R part

Solution to R(r) are

1
é ù2
ê
Rnl (r) = -ê
n -(l -1 ! ) ç ÷
l+ 3
ú æ 2Z ö 2 l - Zr na0 2l+1 æ 2Zr ö
re Ln+l ç ÷
3ú

ë ( )
ê 2néë n + l !ùû ú è
û
na ø è na ø
Restriction on l<n

2 l 1  2 Zr 
Where L n l 
na
 are called associated Laguerre functions
 0
The new quantum number is ‘n’ called principal quantum
number
 Energy of the Hydrogen Atom

Energy is dependent only on ‘n’

Energy obtained by full quantum mechanical treatment is

equal to Bohr energy

Potential energy term is only dependent on the Radial

part and has no contribution from the Angular parts
 Quantum Numbers of Hydrogen Atom
n Principal Quantum number
Specifies the energy of the electron

l Orbital Angular Momentum Quantum number

Specifies the magnitude of the electron's orbital angular
momentum

m Z-component of Angular Momentum Quantum number

Specifies the orientation of the electron's orbital
angular momentum

s Orbital Angular Momentum Quantum number

Specifies the orientation of the electron's spin angular
momentum