3.

012 Fund of Mat Sci: Bonding – Lecture 9

VARIATIONS

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Homework for Fri Oct 14
• Study: 21.4, 23.3
• Read: 23.4, 24.1, 24.2

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Last time:
1. Screening, and coupled, self-consistent
Hartree equations for many-electron atoms
2. 4th quantum number: spin
3. Filling (auf-bau) of the periodic table
4. Physical trends on sizes, IP, EA. (e.g., why He
is smaller than H)

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Variational Principle

Ψ Ĥ Ψ
E [Ψ ] =
Ψ Ψ

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Variational Principle

Ψ Ĥ Ψ
E [Ψ ] =
Ψ Ψ
E [ Ψ ] ≥ E0
If E [ Ψ ] = E0 , then Φ is the ground
state wavefunction, and viceversa…
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Atomic Units
• me=1, e=1, a0 (Bohr radius)=1, h = 1

1
ε0 =
4π
1 Z2
Energy of 1s electron= −
2 n2
(1 atomic unit of energy=1 Hartree=2 Rydberg=27.21 eV

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Energy of an Hydrogen Atom

Ψ Ĥ Ψ
E=
Ψ Ψ

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Energy of an Hydrogen Atom

Ψα Ĥ Ψα
Eα =
Ψα Ψα

Ψα = C exp ( −α r )

C2 1 2 C2 1 C2
Ψα Ψα = π , Ψα − ∇ Ψα = π Ψα − Ψ α = −π 2
α 3
2 2α r α

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Hydrogen Molecular Ion H2+

⎡ ⎛ ⎞⎤ r
⎢− ∇2 + ⎜ r 1 r − 1 r − 1 r
1 ⎟ ⎥ψ (r ) = Eψ (rr )
⎢ 2 ⎜ RA − RB r − RA r − RB ⎟⎥
⎣ ⎝ ⎠⎦

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Linear Combination of Atomic Orbitals
• Most common approach to find out the ground-
state solution – it allows a meaningful definition
of “hybridization”, “bonding” and “anti-bonding”
orbitals.
• Also knows as LCAO, LCAO-MO (for molecular
orbitals), or tight-binding (for solids)
• Trial wavefunction is a linear combination of
atomic orbitals – the variational parameters are the
coefficients:
r r r r
Ψ trial = c1Ψ1s ( )
r − RA + c2 Ψ1s r − RB ( )
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Linear Combination of Atomic Orbitals
r r r r
Ψ trial = c1Ψ1s ( )
r − RA + c2 Ψ1s r − RB ( )

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Bonding and Antibonding (I)

Image of the orbital region for LCAO molecular orbitals removed for copyright reasons.
See Mortimer, R. G. Physical Chemistry. 2nd ed. San Diego, CA: Elsevier, 2000, p. 657, figure 18.7.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Hydrogen Molecular Ion H2+

• Born-Oppenheimer approximation: the

electron is always in the ground state
corresponding to the instantaneous ionic
positions

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)