Hydrogen atom wavefunctions: s orbitals

The Hydrogen atom problem in spherical polar

coordinates
1 ∂ " 2 ∂R % 2µrQZe2 2µr 2
$r '+ 2
+ 2 Ee = β
R ∂r # ∂r & ! !
1
" $2 l+ 3
( )
& n − l −1 ! ' ( 2Z + 2 l − Zr na0 2l+1 ( 2Zr +
Rnl (r) = −& * - re Ln+l * -
3'
& 2n "# n + l !$% ' ) na , ) na ,
# ( ) %
sinθ ∂ # ∂Θ & 2 2
n = 1, 2, 3… l<n
% sinθ ( + β sin θ = m
Θ ∂θ $ ∂θ '
(−1)m m d l+m
Pl (cosθ ) = l (1 − cos θ ) 2 l+m (cos2 θ −1)l
m 2

2 l! dx
(l − m)! m
Pl −m (cosθ ) = (−1)m Pl (cosθ ) with β = l(l +1)
(l + m)!

1 ∂2Φ 2
l=0,1,2,3… |m|< l
= −m
Φ ∂φ 2 Φ(φ ) = Ae ±imφ m=0, ±1, ±2, ±3, ±4,….
 Energy and Angular Momentum

2Q 2 Z 2µe 4 Z 2µe 4 Z 2e 4
En = −
!n 2 2
=− 2 2 2 =−
8ε0 h n 8πε0a0n 2 (
µ ≈ me )
1
" $2 l+ 3

En =
−13.6eV ( )
& n − l −1 ! ' ( 2Z + 2 l − Zr na0 2l+1 ( 2Zr +
Rnl (r) = −& * - re Ln+l * -
3'
n2 & 2n "# n + l !$% ' ) na , ) na ,
# ( ) %
n = 1, 2, 3… l<n
(−1)m m d l+m
Pl (cosθ ) = l (1 − cos θ ) 2 l+m (cos2 θ −1)l
m 2

2 l! dx
(l − m)! m
Pl −m (cosθ ) = (−1)m Pl (cosθ ) with β = l(l +1)
(l + m)!
!! = !ℏ
l=0,1,2,3… |m|< l
Φ(φ ) = Ae ±imφ m=0, ±1, ±2, ±3, ±4,….
 Radial and angular parts

ψ ( r, θ , φ ) = Rn,l ( r ) Θl,m (θ ) Φ m (φ ) = Rn,l ( r ) Yl m (θ , φ )

1
" $2 l+ 3
( )
& n − l −1 ! ' ( 2Z + 2 l − Zr na0 2l+1 ( 2Zr +
Rnl (r) = −& * - re Ln+l * -
3'
& 2n "# n + l !$% ' ) na , ) na ,
# ( ) %
n = 1, 2, 3… l<n
(−1)m m d l+m
Pl (cosθ ) = l (1 − cos θ ) 2 l+m (cos2 θ −1)l
m 2

m 2 l!(2l +1) (l − m)! dx

Yl (θ ,φ ) = Pl m (cosθ )e imφ
(l − m)! m
Pl −m (cosθ ) = (−1)m4π (l +Pm)! l
(cosθ ) with β = l(l +1)
(l + m)!

l=0,1,2,3… |m|< l
Φ(φ ) = Ae ±imφ m=0, ±1, ±2, ±3, ±4,….
Radial Functions of Hydrogen Atom
1
3
é ( n - l - 1 )! ù 2 æ l+
ö 2 l -r na0 2l +1 æ 2r ö
2
Rnl (r ) = - ê ú ç ÷ re Ln +l ç ÷
ê 2n é( n + l )!ù ú è na0 ø
3
na
è 0ø
ë ë û û
32
æ 1 ö -r
n = 1;l = 0 2ç ÷ e ao
2 Zr
è ao ø r=
32
na
1 æ 1 ö æ r ö - r 2 ao
n = 2;l = 0 1 ç ÷ ç2 - ÷e 4pe 0 !2
8 2 è ao ø è a0 ø a=
32
µ e2
1 æ 1 ö æ r ö - r 2 ao
n = 2;l = 1 1 ç ÷ ç ÷e a = a0 (for µ = me )
2 è ao ø è a0 ø
24
æ 1 ö
32
æ 2 é r ù 2 é r ù2 ö - r
n = 3;l = 0 2ç ÷ ç1 - ê ú - ÷ e 3 ao

3a
è oø ç 3 ë a0 û 27 ëê a0 ûú ÷
è ø
32
1 æ 1 ö æ 2r ö - r 3 ao
n = 3;l = 1 1 ç ÷ ç4- ÷e
2 è ao ø è 3a0 ø
486 Number of radial nodes =
32 2
1 æ 1 ö æ 2r ö - r 3ao n-l-1
n = 3;l = 2 1 ç ÷ ç ÷ e
2 è ao ø è 3a0 ø
2430
Probability: Volume element in spherical
polar coordinates

For a s orbital

2 2p

! ! !!
=! !! ! ! !" Θ! !"#!!"! Φ∗ Φ!"!
! ! !

Radial Probability distribution function

 Radial Distribution Functions
Probability of finding the electron in a shell of thickness dr at radius r =
4π r 2 Rnl2 (r)dr (for s)
r 2 → increasing function
4π r 2 Rnl2 (r)dr → 0 as 4π r 2dr → 0

For s-Orbitals :

• Maximum probability denisty

of finding the electron is on the
nucleus
• Probability of finding the
electron on the nucleus zero
 Radial Distribution Functions r 2 Rnl2 (r)

32
æ 1 ö -r
n = 1;l = 0 2ç ÷ e ao

è ao ø
32
1 æ 1 ö æ r ö - r 2 ao
n = 2;l = 0 1 ç ÷ ç2 - ÷e
2 è ao ø è a0 ø
8
32
1 æ 1 ö æ r ö - r 2 ao
n = 2;l = 1 1 ç ÷ ç ÷e
2 è ao ø è a0 ø
24
æ 1 ö
32
æ 2 é r ù 2 é r ù2 ö - r
n = 3;l = 0 2ç ÷ ç1 - ê ú - ê ú ÷ e 3ao
3a
è oø ç 3 ë a0 û 27 ë a0 û ÷
è ø
32
1 æ 1 ö æ 2r ö - r 3 ao
n = 3;l = 1 1 ç ÷ ç4- ÷e
2 è ao ø è 3a0 ø
486
32 2
1 æ 1 ö æ 2r ö - r 3ao
n = 3;l = 2 1 ç ÷ ç ÷ e
2 è ao ø è 3a0 ø
2430
Information from the radial part

Average value of radius:

r = Ψ ns r Ψ ns

Most probable value of radius:

dP(r)
=0
dr
 Angular Distribution Functions
p-Orbitals
32
1 æ 1 ö æ r ö - r 2ao
y 210 = y 2 p = ç ÷ ç ÷e cosq m = 0 case
z
4 2p è ao ø è a0 ø

Angular part: Polar plot of 2pz --- cosq

q cosq
0 1.000
10 0.985
20 0.940
30 0.866
40 0.766
50 0.643
60 0.500
70 0.342
80 0.174
90 0.000
120 -0.500
150 -0.866
180 -1.000

-r
y 210 = y 2 p = N r e
z
2
cosq
3D and contour representations
 3D and contour representations

Closer lines: Steeper gradient

 1s orbital

3 2
!1 $ − r
ao
ψ1s = 2 ## && e
" ao %

Y. U. Sasidhar
 2s orbital
3/ 2
1 æ Z ö 0æ Zr ö
Y2 s = Y2, 0, 0 = 1/ 2 ç ÷ r ç 2 - ÷ exp(- Zr / 2a)
4(2p ) è a ø è a ø
2a
radial node r=
Z

R2 s
3
(1 / 2 )(Z / a) 2

Y. U. Sasidhar

r/a

Y. U. Sasidhar
 2s orbital
3/ 2
1 æ Z ö 0æ Zr ö
Y2 s = Y2, 0, 0 = 1/ 2 ç ÷ r ç 2 - ÷ exp(- Zr / 2a)
4(2p ) è a ø è a ø
2a
radial node r=
Z

R2 s
3
(1 / 2 )(Z / a) 2

r/a
 2s orbital
3/ 2
1 æ Z ö 0æ Zr ö
Y2 s = Y2, 0, 0 = 1/ 2 ç ÷ r ç 2 - ÷ exp(- Zr / 2a)
4(2p ) è a ø è a ø
2a
radial node r=
Z

radial node

y/a - +
x/a

Y. U. Sasidhar
Y. U. Sasidhar
2s orbital

Y. U. Sasidhar
2s orbital

Y. U. Sasidhar
3s orbital
3/2
1 "Z % 0" Zr Z 2r 2 %
Ψ 3s = Ψ 2,0,0 = 1/2 $ ' r $ 27 −18 + 2 2 ' exp(−Zr / 3a)
81(3π ) # a & # a a &

radial nodes

Y. U. Sasidhar
r/a
3s orbital
3s orbital
Hydrogen atom wavefunctions: p and d orbitals
3s orbital

R vs. r r2R2 vs. r

2pz orbital
5/ 2
1 æZö 1
Y2 p = ç ÷ r exp(- Zr / 2a) cosq Angular Part
(2,1,0) 4 2p èaø
z
cosq = z / r

Radial Part starts with a zero at r=0; so does Y

R2 p a 3 / 2 = (1 / 2 6 ) Z 5 / 2 (r / a) exp(- Zr / 2a)

No radial node !

Y. U. Sasidhar
Y. U. Sasidhar r/a
2pz orbital
5/ 2
1 æZö 1
Y2 p = ç ÷ r exp(- Zr / 2a) cosq Angular Part
(2,1,0) 4 2p èaø
z
cosq = z / r

x
z

Y. U. Sasidhar
2pz orbital
5/ 2
1 æZö 1
Y2 p = ç ÷ r exp(- Zr / 2a) cosq Angular Part
(2,1,0) 4 2p èaø
z
cosq = z / r

x
z

X
Z Y. U. Sasidhar
2pz orbital
5/ 2
1 æZö 1
Y2 p = ç ÷ r exp(- Zr / 2a) cosq
z
4 2p èaø
Angular node
same value z=0

_ + x/a

- ve contours + ve contours

Y. U. Sasidhar
z/a
2pz orbital: Constant Probability Surface

Y. U. Sasidhar
2pz orbital: Probability distribution as dots

Y. U. Sasidhar
2p Orbitals

1 !1 $
3 2
! r $ − r 2a Quantum mechanical
ψ2,1,0 = ψ2 p = ## && ## && e o
cosθ operators are linear
z
4 2π " ao % " a0 %
3 2
1 !1 $ ! r $ − r 2a
ψ2,1,+1 = ψ2 p = ## && ## && e o
sinθ e iφ
+1
8 π " ao % " a0 % Linear
3 2
1 !1 $ ! r $ − r 2a combination
ψ2,1,−1 = ψ2 p = ## && ## && e o
sinθ e −iφ
−1
8 π " ao % " a0 %

3 2
1 !1 $ ! r $ − r 2a 1
ψ2 p
x
= ## &&
32π " ao %
## && e
" a0 %
o
sinθ cos φ =
2
(
ψ2,1,+1 + ψ2,1,−1 )
3 2
1 !1 $ ! r $ − r 2a 1
ψ2 p
y
= ## &&
32π " ao %
## && e
" a0 %
o
sinθ sin φ =
2i
(
ψ2,1,+1 − ψ2,1,−1 )
3pz orbital

æ Zr ö
Y3 pz = ( 2 / 81 p ) Z ( Z / a) 3 / 2 (r 1 / a)ç 6 - ÷ exp(- Zr / 3a) cosq
è a ø
æ Zr ö
R3 p ´ a 3 / 2 = (8 / 27 6 ) Z 5 / 2 (r 1 / a)ç1 - ÷ exp(- Zr / 3a)
è 6a ø
radial
node

Y. U. Sasidhar
r/a
3pz orbital

æ Zr ö
Y3 pz = ( 2 / 81 p ) Z ( Z / a) 3 / 2 (r 1 / a)ç 6 - ÷ exp(- Zr / 3a) cosq
è a ø

radial node

x/a x/a

angular node

z/a y=0 here

3pz orbital

æ Zr ö
Y3 pz = ( 2 / 81 p ) Z ( Z / a) 3 / 2 (r 1 / a)ç 6 - ÷ exp(- Zr / 3a) cosq
è a ø
3pz orbital: Surface of constant probability
3pz orbital: Probability distribution as dots
3d x 2 −y2
3/2 2
1 #Z& #Z& 2 2
Ψ 3d 2 = % ( % ( r exp(−Zr / 3a)sin θ cos2ϕ
x −y 2
81 2π $ a ' $ a '
4 7/2 1
R3 d ´ a 3/ 2
= Z 2
r 2
exp(- Zr / 3a )
81 30 a

r/a
Y. U. Sasidhar
3d x - y
2 2
3/2 2
1 #Z& #Z& 2 2
Ψ 3d 2 = % ( % ( r exp(−Zr / 3a)sin θ cos2ϕ
x −y 2
81 2π $ a ' $ a ' 2
(x - y ) / r
2 2

Angular nodes: x = ± y

-
+ +
y/a
-

x/a
3d xy
3/ 2 2
1 æZ ö æZ ö 2
Y3d = ç ÷ ç ÷ r exp( - Zr / 3a ) sin 2
q sin 2f
xy
81 2p èaø èaø 2
xy / r
angular nodes: x=0, y=0

- +
y/a

+ -

x/a
3d z 2
1 1
Y3dz 2 a 3/ 2
= Z 7/2
r 2 (exp(- Zr / 3a) )(3 cos 2 q - 1)
2

81 6p a z2
(3 2
- 1)
r
2 angular nodes

-
x/a + +

z/a
3d z 2
1 1
Y3dz 2 a 3/ 2
= Z 7/2
r 2 (exp(- Zr / 3a) )(3 cos 2 q - 1)
2

81 6p a z2
(3 2
- 1)
r
2 angular nodes
3dz2 : Surface of constant probability
3dz2 : Surface of constant probability with angular
nodes
3dz2 : Probability distribution as dots
 3d z 2 is only a nickname

1 1
Y3dz 2 a 3/ 2
= Z 7/2
r 2 (exp(- Zr / 3a) )(3 cos 2 q - 1)
2

81 6p a z2
(3 2
- 1)
r

(x2 + y 2 + z 2 )

Full label: 3d 2 z 2 - x 2 - y 2
4f0
4f0 : Nodal Surface in grey
 Surface plots

Surface plot of the 3dz2 wavefunction (orbital) in the xz (or yz) plane for the Surface plot of the (3dz2 )2 the probability density associated with the 3dz2
hydrogen atom. The large hills correspond to the positive lobes and the orbital of the hydrogen atom. This figure is rotated with respect to the
small pits correspond to the negative lobes. figure on the left so that the small hill will be clearly visible. Another
smaller hill is hidden behind the large hill.

Surface plot of the 3dxy wavefunction (orbital) in the xz plane for the
hydrogen atom. The hills and the pits have same amplitude. Surface plot of the (3dxy )2 the probability density associated with the 3dxy
orbital of the hydrogen atom. Pits in the figure to the left appear has hills.
Cross-sections of Orbitals
Hydrogen Wavefunctions
Orbitals: External Structure
Orbitals: Internal Stucture
Hydrogen atom & Orbitals

Hydrogen atom has only one electron, so why bother

about all these orbitals?

1. Excited states
2. Spectra
3. Many electron atoms