M.

Sc Chemistry 2020 - CHEM 412 : UNIT II

Analysis of the Solutions

Of Hydrogenic systems

Musiri M. Balakrishnarajan
Chemical Information Sciences
Pondicherry University.

I do not like it, and I am sorry I

ever had anything to do with it

Erwin Schrödinger
 Hydrogen atom Energy Levels
−1
Energy of Hydrogenic Atom =
2𝑛2

Degeneracy is n2 for a given primary quantum number n Continuum of Unbound States

Result of increased SO(4) symmetry of the system.
0.0
2𝑛+1 n=3
Spacings between the levels reduce with increasing n ΔE = 2𝑛2 𝑛+1 2
n=2
Implies finite ionization energy
Potential Energy
Unlike particle in a box or harmonic oscillator.

Energy (a.u)→
Increasing the n increases the effective potential barrier
−𝑒 2
V= .
4𝜋ε0 𝑟
V is negatively infinite when r→0 and becomes 0 when r → ∞ 0.5 n=1
Particle Penetrates the Potential energy barrier (Tunneling)
r →

𝑍𝑒𝑟𝑜 𝑝𝑜𝑖𝑛𝑡 𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑠 𝑛𝑜𝑡 𝑧𝑒𝑟𝑜, 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑚𝑜𝑣𝑒𝑠 𝑎𝑟𝑜𝑢𝑛𝑑 𝑒𝑣𝑒𝑛 𝑎𝑡 0𝐾.
 Solutions of Schrodinger Equation
The general solution for the bound state of hydrogenic atom is

𝜓 (𝑟, θ, 𝝋 ) = 𝜓𝑟 (𝑟) . 𝜓θ(θ) . 𝜓𝝋(𝝋 )

ψ𝑛𝑙𝑚𝑙 = 𝑅𝑛,𝑙 (𝑟) . Yl, m(θ, 𝝋) .

2𝑟 2𝑟 − 2𝑙+1
3 𝑙 − 𝑛−𝑙−1 𝑛+𝑙
2 (𝑛 − 𝑙 − 1)! 𝑟
− 𝑛𝑎 2𝑟 𝑒 𝑛𝑎 𝑛𝑎 𝑑 2𝑟
− 𝑛𝑎 2𝑟
ψ𝑛𝑙𝑚𝑙 = 𝑒 𝑒 .
𝑛𝑎 2𝑛 𝑛 + 𝑙 ! 3 𝑛𝑎 𝑛−𝑙−1 ! 2𝑟 𝑛−𝑙−1 𝑛𝑎
𝑑
𝑛𝑎
𝑚
𝑑 |𝑚| 1 𝑑𝑙 2𝑙+1 (𝑙−𝑚)! −𝑖𝑚𝝋
1− cos 2 θ 2 cos 2 θ − 1 𝑙 . 𝑒
𝑑(cos θ)|𝑚| 2!𝑙! 𝑑(cos θ)𝑙 4𝜋 𝑙+𝑚 !

Which looks really long and complex but still decipherable since the simplification of the entire factor is not done.

𝑆𝑐ℎ𝑟𝑜𝑑𝑖𝑛𝑔𝑒𝑟 𝑑𝑜 ℎ𝑎𝑣𝑒 𝑎𝑛 𝑒𝑥𝑡𝑟𝑎𝑜𝑟𝑑𝑖𝑛𝑎𝑟𝑦 𝑔𝑖𝑓𝑡 𝑜𝑓 ℎ𝑎𝑛𝑑𝑙𝑖𝑛𝑔 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 𝑠𝑖𝑡𝑢𝑎𝑡𝑖𝑜𝑛𝑠!

 Wave functions of Hydrogen Atom
Radial part R(r) Theta part T(θ) Pi part Combined Form
2 𝑟 1 1 3/2
𝑒
− 1 1 𝑟
− 𝑎
1s (ψ100 ) a3/2
𝑎
2 2𝜋 . 𝑒
𝜋 a
3 3
1 1 2 𝑟 − 𝑟 1 1 1 1 2 𝑟 − 𝑟
2s (ψ200 ) 2− 𝑒 2𝑎 . 2− 𝑒 2𝑎
2 2 a 𝑎 2 2𝜋 4 2𝜋 a 𝑎
3 3
6 1 11 2 𝑟 − 𝑟
1 1 2 r − 𝑟
𝑐𝑜𝑠θ . 𝑒 2𝑎 𝑐𝑜𝑠θ
2𝑝0 (ψ210 ) . 𝑒 2𝑎
2 2𝜋 4 2𝜋 a 𝑎
2 6 a a
3 3
1 1 2 r − 𝑟 3 1 1 1 2 𝑟 − 𝑟
𝑒 −𝑖𝝋 . 𝑒 2𝑎 𝑠𝑖𝑛θ 𝑒 −𝑖𝝋
2𝑝−1 (ψ21−1 ) . 𝑒 2𝑎
2
𝑠𝑖𝑛θ 2𝜋 8 𝜋 a 𝑎
2 6 a a
3
3
3 1 11 2 𝑟 − 𝑟
1 1 2 r − 𝑟
𝑒 𝑖𝝋 − . 𝑒 2𝑎 𝑠𝑖𝑛θ 𝑒 𝑖𝝋
2𝑝+1 (ψ211 ) − . 𝑒 2𝑎
2
𝑠𝑖𝑛θ 2𝜋 8 𝜋 a 𝑎
2 6 a a
3
𝑟
1 1 1 2 𝑟 −
2𝑝𝑥 = (2𝑝+1 + 2𝑝−1 ) = . 𝑒 2𝑎 𝑠𝑖𝑛θ 𝑐𝑜𝑠𝝋
2 4 2𝜋 a 𝑎
Chemical Orbitals 3
𝑟
1 1 1 2 𝑟 −
2𝑝𝑦 = (2𝑝+1 − 2𝑝−1 ) = . 𝑒 2𝑎 𝑠𝑖𝑛θ 𝑠𝑖𝑛𝝋
2 4 2𝜋 a 𝑎
 Wave functions of Hydrogen Atom contd.
R(r) T(θ) P(𝝋) ψ𝑛𝑙𝑚 (𝑟, θ, 𝝋)
3 3
1 1 2 1 2 r r2 𝑟
2 1 2 r r2 −
𝑟 − 3𝑎
3s 27 − 18 + 2 2 𝑒 3𝑎 2 27 − 18 + 2 2 𝑒
a a a 2𝜋 81 3𝜋 a a a
81 3
3
3 1
4 1 2 𝑟 𝑟 − 𝑟 6 2 1 2 𝑟 𝑟 − 𝑟
3𝑝0 6− 𝑒 3𝑎 𝑐𝑜𝑠θ 2𝜋
81 𝜋 a
6−
𝑎 𝑎
𝑒 3𝑎 𝑐𝑜𝑠θ
81 6 a 𝑎 𝑎 2
3 3
1
4 1 2 𝑟 𝑟 − 𝑟 3 𝑒 𝑖𝝋 1 1 2 𝑟 𝑟 − 𝑟
3𝑝1 6− 𝑒 3𝑎 𝑠𝑖𝑛θ 2𝜋 6− 𝑒 3𝑎 𝑠𝑖𝑛θ 𝑒 𝑖𝝋
81 6 a 𝑎 𝑎 2 81 𝜋 a 𝑎 𝑎
3
10 1 3
2 1 1 2 𝑟 2 𝑟
4 1 2 𝑟 𝑟
− 3𝑎 (3 cos 2 θ − 1) − 3𝑎
(3 cos2 θ − 1)
3𝑑0 𝑒 4 2𝜋
a 𝑎
𝑒
81 30 a 𝑎 81 6𝜋
3 3
1
𝑒 𝑖𝝋
4 1 2 𝑟 2 𝑟 15 2
1 1 2 𝑟 𝑟
𝑠𝑖𝑛θ cos θ 𝑒 𝑖𝝋
− 3𝑎
3𝑑1 𝑒 𝑠𝑖𝑛θ 𝑐𝑜𝑠θ 2𝜋 . 𝑒
− 3𝑎
81 30 a 𝑎 2 81 𝜋 a 𝑎
3 3
4 1 2 𝑟 2 𝑟 1 2
𝑒 2𝑖𝝋
15 2 1 1 2 𝑟 𝑟
sin2 θ 𝑒 2𝑖𝝋
− 3𝑎 − 3𝑎
3𝑑2 a 𝑎
𝑒 sin θ . 𝑒
81 30 2 2𝜋 162 𝜋 a 𝑎

*Phase factor is omitted

 Average Values of Kinetic Energy in the Ground state
1 Z 3/2 −
𝑟
1 1 3/2 −
𝑟
The general solution for the ground state is ψ1𝑠 = . 𝑒 𝑎 . For the Hydrogen atom 1s = . 𝑒 𝑎
𝜋 a 𝜋 a

1
Average Kinetic Energy, < T > = − ‫ ׬‬ψ1𝑠
∗
− 2μ ∇2 ψ1𝑠 𝑑𝞽
2 𝑑2 𝑅 2 𝑑𝑅 𝐿2 4𝜋2
∇ 𝑅= + − 𝑅 =0
1 ∗
𝑑𝑟 2 𝑟 𝑑𝑟 r2 ℎ 2
< 𝑇 > = − ම ψ1𝑠 ∇2 ψ1𝑠 𝑟 2 𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ𝑑𝝋
2μ 𝐿2 𝑅 = 𝑙 𝑙 + 1 𝑅, but for 1s, l=0,
2
1 ∗
𝑑 2𝑑 𝑑2 𝑅 2 𝑑𝑅
= − ම ψ1𝑠 2
+ ψ1𝑠 𝑟 2 𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ𝑑𝝋 hence ∇ 𝑅 = 2
+ 𝑟 𝑑𝑟
2μ 𝑑𝑟 𝑟 𝑑𝑟 𝑑𝑟 2

3/2 3/2
1 2𝜋 𝜋 ∞ 1 1 𝑟
− 𝑎 𝑑2 2 𝑑 1 1 𝑟
− 𝑎 1 1 3/2 −
𝑟
=− න න න . 𝑒 + . 𝑒 𝑟 2 𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ𝑑𝝋 ψ1𝑠 = . 𝑒 𝑎
2μ 0 0 0 𝑑𝑟 2 𝑟 𝑑𝑟 𝜋 a
𝜋 a 𝜋 a
𝑑ψ1𝑠 1 1 5/2 −
𝑟

1 2𝜋 𝜋 ∞ 𝑟 𝑑2 2 𝑑 𝑟 =− . 𝑒 𝑎
− − 𝑑𝑟 𝜋 a
=− න 𝑑𝝋 න 𝑠𝑖𝑛θ 𝑑θ න 𝑒 𝑎 + 𝑒 𝑎 𝑟 2 𝑑𝑟
2μ𝜋𝑎3 0 0 0 𝑑𝑟 2 𝑟 𝑑𝑟 𝑑2 ψ1𝑠 1 1 7/2 𝑟
−
= . 𝑒 𝑎
𝑑𝑟 2 𝜋 a
1 2𝜋 𝜋 ∞ 𝑟 𝑑2 2 𝑑 𝑟
− −
=− න 𝑑𝝋 න 𝑠𝑖𝑛θ 𝑑θ න 𝑒 𝑎 + 𝑒 𝑎 𝑟 2 𝑑𝑟
2μ𝜋𝑎3 0 0 0 𝑑𝑟 2 𝑟 𝑑𝑟 𝑛!
න 𝑥 𝑛 𝑒 −𝑞𝑥 𝑑𝑥 = , 𝑤ℎ𝑒𝑟𝑒 𝑛 ≻ 1 𝑎𝑛𝑑 𝑞 > 0
𝑞 𝑛+1
1
=
2
a. u < T1s > = −E1s 𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝐾𝑖𝑛𝑒𝑡𝑖𝑐 𝑒𝑛𝑒𝑟𝑔𝑦 𝑒𝑞𝑢𝑎𝑙 𝑡𝑜 𝑡ℎ𝑒 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦
 Average Value of Potential Energy: Virial theorem
1 Z 3/2 −
𝑟
1 1 3/2 −
𝑟
The general solution for the ground state is ψ1𝑠 = . 𝑒 𝑎 . For the Hydrogen atom 1s = . 𝑒 𝑎
𝜋 a 𝜋 a
∗ 1
Average Potential Energy, < V1s > = − ‫ ׬‬ψ1𝑠 ψ
𝑟 1𝑠
Inter-Relationship between Components
3/2 3/2
1 1 𝑟
− 𝑎 1 1 1 𝑟
− 𝑎 1
= −න . 𝑒 . 𝑒 < E > = − a. u
𝜋 a 𝑟 𝜋 a 2
1 2𝜋 𝜋 ∞ 𝑟 1 − 𝑟 1
= − 3න න න 𝑒
−
𝑎 𝑒 𝑎 𝑟 2 𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ𝑑𝝋 < T > = a. u
𝜋𝑎 0 0 0 𝑟 2

2𝜋 𝜋 ∞ < V > = −1 a. u
1 −
2𝑟
=− න 𝑑𝝋 න 𝑠𝑖𝑛θ 𝑑θ න 𝑒 𝑎 𝑟 2 𝑑𝑟 <E>=<T>+<V>
2μ𝜋𝑎3 0 0 0
1 <V>
𝑛!
< T >= −2 < V > or = −2
= −1 a. u <T>
න 𝑥 𝑛 𝑒 −𝑞𝑥 𝑑𝑥 = , 𝑤ℎ𝑒𝑟𝑒 𝑛 ≻ 1 𝑎𝑛𝑑 𝑞 > 0
𝑞 𝑛+1
Virial theorem
< V1s > = 2E1s The Average (expectation) value of potential
General Formula for hydrogenic system energy is twice the negative of the kinetic energy
1 𝑧
< >= 2
𝑟 𝑛 𝑎 True for not just ground state, but all bound states

𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑠 𝑡𝑤𝑖𝑐𝑒 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 Derives from Euler’s theorem of homogenous functions
 Angular Momentum Basics
Angular Momentum vector
In Classical Mechanics L = 𝑟Ԧ 𝑋 𝑝Ԧ 𝑝Ԧ
𝑟Ԧ L = iLx + jLy + kLz
Where its cartesian components are
Lx= ypz- zpy, LY= zpx- xpz, Lz= xpy- ypx, The Square of the Angular momentum
In Quantum Mechanics, the corresponding operators are L2 = L. L = Lx . Lx + Ly . Ly + Lz . Lz

ih δ ih δ ih δ = Lx .2 +L2y + L2z
px = − py = − pz = −
2𝜋 δ𝑥 2𝜋 δ𝑦 2𝜋 δ𝑧 The square of the angular momentum commutes with
cartesian components. Their eigen functions are same.
−ih δ δ −ih δ δ
Lx = y δ𝑧 − 𝑧 δ𝑦 Ly = z δ𝑥 − 𝑥 δ𝑧 Lz =
−ih δ
x δ𝑦 − 𝑦 δ𝑥
δ [𝐿2 , 𝐿𝑥 ] = [𝐿2 , 𝐿𝑦 ] = [𝐿2 , 𝐿𝑧 ] =0
2𝜋 2𝜋 2𝜋

The individual components of the angular momentum do not

Angular Momentum in spherical polar coordinates
commute with each other. They cannot be determined accurately.
ih ℎ 2 1 𝜕 𝜕 1 𝜕 2
𝐿𝑥 , 𝐿𝑦 = − 𝐿 ; 𝐿2 = − 2 𝑆𝑖𝑛θ + 2
2𝜋 𝑧 4𝜋 𝑠𝑖𝑛θ 𝜕θ 𝜕θ sin θ 𝜕 2 𝝋
ih
𝐿𝑦 , 𝐿𝑧 = − 𝐿𝑥 ;
2𝜋 ih 𝜕 h 2 𝜕2
ih Lz = − L2z =
[𝐿𝑧 , 𝐿𝑥 ] = − 𝐿 2𝜋 𝜕𝝋 4𝜋 2 𝜕 2 𝝋
2𝜋 𝑦
 Angular momentum from the Angular Part
The Angular Momentum in spherical polar coordinates is given by And the z component is given by
ℎ 2 1 𝜕 𝜕 1 𝜕 2 ih 𝜕 h2 𝜕 2
𝐿2 = − 2 𝑆𝑖𝑛θ + 2 Lz = − L2z =− 2 2
4𝜋 𝑠𝑖𝑛θ 𝜕θ 𝜕θ sin θ 𝜕 2 𝝋 2𝜋 𝜕𝝋 4𝜋 𝜕 𝝋

The Angular part of the Hydrogen atom Schrodinger eqation is The 𝜑 part of the Schrodinger eqation is

1. 𝜕 𝜕𝐴 θ, 𝝋 1 𝜕 2 𝐴 θ, 𝝋 𝜕2𝑃 𝜑
𝑠𝑖𝑛θ + 2 = −𝑙 𝑙 + 1 𝐴 θ, 𝝋 = − m2 𝑃 𝜑
𝑠𝑖𝑛 θ 𝜕θ 𝜕θ sin θ 𝜕φ2 𝜕φ 2

Substituting L2 in this equation gives Substituting L2z in this equation gives

𝐿2 𝐴 θ, 𝝋 =
ℎ2
𝑙 𝑙+1 𝐴 θ, 𝝋 h2
4𝜋2 L2z 𝑃 𝜑 = 2 𝑚2 𝑃 𝜑
4𝜋
The 𝑙 𝑙 + 1 is the eigen value of the Square Hence, ± m is the eigen value of the z
of angular momentum operator component of the angular momentum operator

The x and y components of the angular momentum operators do not have eigen values associated with them.
Correlates with the non-commutativity of individual components, i.e., only one component can be determined.

𝑇ℎ𝑒 𝑒𝑥𝑝𝑒𝑐𝑎𝑡𝑖𝑜𝑛 𝑣𝑎𝑙𝑢𝑒𝑠 𝑜𝑓 𝐿2 𝑎𝑛𝑑 𝐿𝑍 𝑐𝑎𝑛 𝑏𝑒 𝑎𝑟𝑟𝑖𝑣𝑒𝑑 𝑑𝑖𝑟𝑒𝑐𝑡𝑙𝑦 𝑢𝑠𝑖𝑛𝑔 𝐿𝑎𝑑𝑑𝑒𝑟 𝑜𝑝𝑒𝑟𝑎𝑡𝑜𝑟𝑠
Angular momentum: Vector Atom model of Hydrogen in d orbital
Radius of the sphere : 𝑙(𝑙 + 1)
Z axis Projection of the L: ml
−1 ml h
ml=+2
Angle of inclination of L : θ = cos ( )
𝑙 𝑙+1 2𝜋
Components of the L vector in x,y directions : undefined
ml = +1

θ Z-axis
ml = 0 |L|=l*l(+1)

ml = -1

ml=-2
𝐹𝑖𝑥𝑖𝑛𝑔 𝐿𝑧 𝑙𝑒𝑎𝑑𝑠 𝑡𝑜 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝐿𝑥, 𝑎𝑛𝑑 𝐿𝑦

Space Quantization
Only certain Orientations of L (values of θ ) are allowed Unique for Quantum mechanics.
 Average and Most Probable distance of the electron from the nucleus
Average distance for an electron in ψ𝒏𝒍𝒎, Most Probable distance for an electron in ψ𝒏𝒍𝒎,
For the Ground State 1s it is < 𝑟 > = < ψ𝑛𝑙𝑚 𝑟 ψ𝑛𝑙𝑚 > Probability of finding an electron in ψ𝑛𝑙𝑚 is ψ2𝑛𝑙𝑚 (r)
∗
< 𝑟 > = න ψ1𝑠 𝑟 ψ1𝑠 𝑑𝞽 Probability of finding an electron at distance r is 4𝜋𝑟 2 ψ2𝑛𝑙𝑚 (r)
3/2 3/2 The most probable distance of finding an electron is where
1 1 𝑟
− 𝑎 1 1 𝑟
− 𝑎
=න 𝑒 𝑟 𝑒 𝑟 2 𝑑𝑟𝑠𝑖𝑛θ𝑑θ𝑑𝝋 𝑑 2
𝜋 a 𝜋 a ψ (r) =0
𝑑𝑟 𝑛𝑙𝑚
2𝜋 𝜋 ∞ For the Ground State 1s it is
1 −
𝑟 𝑟
− 𝑎
= 3න න න 𝑒 𝑎 𝑟 𝑒 𝑟 2 𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ𝑑𝝋
𝜋𝑎 0 0 0 𝑑 1 1 3 − 2𝑟
2
(4𝜋𝑟 ) 𝜋 a 𝑒 𝑎 =0
2𝜋 𝜋 ∞ 𝑑𝑟
1 −
2𝑟
= 3න 𝑑𝝋 න 𝑠𝑖𝑛θ 𝑑θ න 𝑒 𝑎 𝑟 3 𝑑𝑟 2𝑟 2 − 2𝑟
𝜋𝑎 0 0 0 (2𝑟 − )𝑒 𝑎 =0
3 𝑎
= a (a. u) 𝑟𝑚𝑝 = 𝑎
2
General Formula for hydrogenic system The most probable distance between the electron and nuclei is
𝑛2 𝑎 1 𝑙 𝑙+1 equal to a, which is the Bohr’ radius in Bohr atom model
<𝑟 >= 1+ 1− (except for reduced mass)
𝑧 2 𝑛2

3
𝑇ℎ𝑒 𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑖𝑛 1𝑆 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 𝑖𝑠 𝑡𝑖𝑚𝑒𝑠 𝑡ℎ𝑒 𝑚𝑜𝑠𝑡 𝑝𝑟𝑜𝑏𝑎𝑏𝑙𝑒 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒
2
 Hydrogen atom Ground State: Scatter plots and Contours

Probability Density Reduces when moving away from the nuclei (increasing r)
Most probable distance value is not at the nuclei, at a
Average distance value is not at the nuclei, at 3a/2
 Hydrogen atom s orbitals: Scatter plots and Contours
3/2
1 1 −
𝑟
. 𝑒 𝑎
𝜋 a
3
1 1 2 𝑟 − 𝑟
. 2− 𝑒 2𝑎
4 2𝜋 a 𝑎
3
2 1 2 r r2 −
𝑟
27 − 18 + 2 2 𝑒 3𝑎
81 3𝜋 a a a

Maximum probability
Moves away from the nuclei
With increasing n

Orbitals become more diffuse

With increasing n

Radial nodes maintains the

Orthogonality between orbitals
Radial Plots for Hydrogen Atom Wavefunctions
 0.6 Solving the ρ Equation (Asymptotic)
Radial Distribution Plots for Hydrogen AOs
0.5

1S
0.4 2S
2p
_𝑛𝑙𝑚^2(r)

35
0.3
Radial Distribution"ψ"

3p
3d
0.2
4s
4p
0.1 4d
4f
0
0 Ristance r →
 P Orbital Shapes : Polar Plots

𝜋
θ Cos(θ) 𝜋
0 1
15 0.965925826
30 0.866025404
45 0.707106781
60 0.5
75 0.258819045 3𝜋
𝜋 3𝜋
2 𝜋
90 0.0 2 2
2
105 -0.258819045
120 -0.5
135 -0.707106781
150 -0.866025404
165 -0.965925826
180 -1 0 0
 Polar Plots of d0 Orbital
𝜋 𝜋

3𝜋 𝜋 3𝜋 𝜋
2 2 2 2

0 0
 Directional Properties of Orbitals: Linear combination of vectors
𝑛𝑝0 = 𝑁. 𝑟. 𝑒 𝑧𝑟/2𝑎 cos 𝜃 𝑛𝑝𝑧 = 𝑁. 𝑟. 𝑒 𝑧𝑟/𝑛𝑎 cos 𝜃
1 𝑁
n𝑝+1 = 𝑁. 𝑟. 𝑒 𝑧𝑟/2𝑎 sin 𝜃 𝑒 𝑖𝝋 𝑛𝑝𝑥 = . 2𝑝+1 − 2𝑝−1 = 𝑟. 𝑒 𝑧𝑟/𝑛𝑎 sin 𝜃 cos 𝝋
2 2
1 𝑁
𝑛𝑝−1 = 𝑁. 𝑟. 𝑒 𝑧𝑟/2𝑎 sin 𝜃 𝑒 −𝑖𝝋 𝑛𝑝𝑦 = . 2𝑝+1 + 2𝑝−1 = 𝑟. 𝑒 𝑧𝑟/𝑛𝑎 sin 𝜃 sin 𝝋
2 2
1 1
𝑛𝑑0 = 𝑁. 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 (3cos 2 𝜃 − 1) 𝑛𝑑𝑧 2 = 𝑁. 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 (3cos 2 𝜃 − 1)
3 3
1 𝑁 2 𝑧𝑟/𝑛𝑎
n𝑑+1 = 𝑁. 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 sin2 𝜃 𝑒 𝑖𝝋 𝑛𝑑𝑥𝑧 = . 𝑛𝑑+1 − 𝑛𝑑−1 = .𝑟 .𝑒 sin2𝜃 cos 𝝋
2 2
1 𝑁 2 𝑧𝑟/𝑛𝑎
𝑛𝑑−1 = 𝑁. 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 sin2 𝜃𝑒 −𝑖𝝋 𝑛𝑑𝑦𝑧 = . 𝑛𝑑+1 + 𝑛𝑑−1 = .𝑟 .𝑒 sin2𝜃 sin 𝝋
2 2
1 𝑁
𝑛𝑑+2 = 𝑁. 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 sin2𝜃𝑒 2𝑖𝝋 n𝑑𝑥2−𝑦2 = . 𝑛𝑑+2 − 𝑛𝑑−2 = . 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 sin2 𝜃 cos 𝟐𝝋
2 2
1 𝑁
𝑛𝑑−2 = 𝑁. 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 sin2𝜃 𝑒 −2𝑖𝝋 𝑛𝑑𝑥𝑦 = . 𝑛𝑑+2 + 𝑛𝑑−2 = . 𝑟 2 . 𝑒 𝑧𝑟/𝑛𝑎 sin2 𝜃 s𝒊𝒏 𝟐𝝋
2 2

Three planar nodes 𝑑𝑥 2−𝑦2 , 𝑑𝑧 2 −𝑦2 , 𝑑𝑧 2 −𝑥 2 are not linearly independent, i.e., (𝑧 2 − 𝑦 2 ) − (𝑧 2 − 𝑥 2 ) = 𝑥 2 − 𝑦 2 . Hence
the positive combination i.e., (𝑧 2 − 𝑦 2 ) + (𝑧 2 − 𝑥 2 ) = 2𝑧 2 − 𝑥 2 − 𝑦 2 = 3𝑧 2 − 𝑟 2 is used and referred as 𝑑𝑧 2
 Distinct Real Orbital Shapes for n=4

4s 4p 4𝑑𝑧 2 4𝑑𝑥𝑧 4𝑑𝑦𝑧 4𝑑𝑥𝑦 4𝑑x2 −y2

4𝑓𝑧 3 4𝑓𝑦𝑧 2 4𝑑𝑥𝑧 2 4𝑓𝑧(𝑥 2 −𝑦 2) 4𝑓𝑦(3𝑥 2−𝑦2) 4𝑑𝑥(𝑥 2−3𝑦2) 4𝑓𝑥𝑦𝑧

Contour plots
 Scatter Plots of some l=0 excited states

5d0 4p0 2p0

5f0 4d0 3p0

5g0 4f0 3d0

 Drum plots
1s 2s 3s

2p 3p 4p

3d 4d 5d
The End