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 (2m) + i sin (2m) = 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 (2m) + i sin (2m) = 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
