Quantum Mechanics/Chemistry: Agenda

Postulates & Schrdinger equation (Engel, Ch. 2-3) Simple model systems Particle in a box (Ch. 4-5) Harmonic oscillator (vibration) (Ch. 7-8) Particle on a ring or a sphere (rotation) (Ch 7 8) (Ch. 7-8) Real chemical systems Hydrogen atom (one electron atom) (Ch. 9) (one-electron Many-electron atoms (Ch. 10-11) Diatomic molecules (Ch. 12-13) Polyatomic molecules (Ch. 14) Computational chemistry (Ch. 16)

Postulates in Quantum Mechanics

References
Engel, Ch. 2-3 Molecular Quantum Mechanics, Atkins & Friedman (4th ed. 2005), Ch. 1 Introductory Quantum Mechanics, R. L. Liboff (4th ed, 2004), Ch. 3 A Brief Review of Elementary Quantum Chemistry http://vergil.chemistry.gatech.edu/notes/quantrev/quantrev.html Wikipedia (http://en.wikipedia.org): Search for Wave function Measurement in quantum mechanics Expectation value (quantum mechanics) Schrodinger equation

Postulate #1 of Quantum Mechanics

The state of a quantum mechanical system is completely specified by the wavefunction or state function ( r , t ) that depends on the coordinates of the particle(s) and on time. The probability to find the particle in the volume element d = drdt located at r at time t is given by ( r , t ) ( r , t ) d . (Born interpretation) The wavefunction must be single-valued, continuous, finite, and normalized (the probability of find it somewhere is 1).

d (r , t )

| = 1 = <|>

Probability density e s

Born Interpretation of the Wavefunction: Probability Density

Postulates #2 & #3 of Quantum Mechanics

Once ( r , t ) is known, all properties of the system can be obtained known by applying the corresponding operators to the wavefunction. Observed in measurements are only the eigenvalues a which satisfy the eigenvalue equation

A = a

eigenvalue i l

eigenfunction i f i

(Operator)(function) = (constant number)(the same function) (Operator corresponding to observable) = (value of observable)

Observables, Operators & Solving Eigenvalue Equations: an Example

= Ae ikx
px = h d i dx

h d = p x i dx h d Ae ikx = khAe ikx = kh i dx constant

the same function

p x = + kh

number

The Schrdinger Equation

Hamiltonian operator energy & wavefunction (solving ( l i a partial differential equation) ti l diff ti l ti )
with ( (Hamiltonian operator) p )

(e.g. with (1-dim)

The ultimate goal of most quantum chemistry approach is the solution of the time-independent Schrdinger equation time independent equation.

Quantum Mechanics/Chemistry: Agenda

Postulates & Schrdinger equation (Ch. 2-3)

Simple model systems = Simple examples of V(r) Particle in a box (Ch. 4-5) Harmonic oscillator (vibration) (Ch. 7-8) Particle on a ring or a sphere (rotation) (Ch. 7-8) l h ( ) (Ch 8) Real chemical systems Hydrogen atom (one electron atom) (Ch 9) (one-electron (Ch. Many-electron atoms (Ch. 10-11) Diatomic molecules (Ch. 12-13) Polyatomic molecules (Ch. 14) Computational chemistry (Ch. 16)

Simple Systems
Particle in a box (infinite or finite) (translation) Harmonic oscillator (vibration)
V = 1 2 kx 2

Particle on a ring or a sphere (rotation)

k : force constant

Simple Model for Translational Motion

References
Engel, Ch. 4-5 Molecular Quantum Mechanics, Atkins & Friedman (4th ed. 2005), Ch. 2 Introductory Quantum Mechanics, R. L. Liboff (4th ed, 2004), Ch. 4 A Brief Review of Elementary Quantum Chemistry http://vergil.chemistry.gatech.edu/notes/quantrev/quantrev.html Wikipedia (http://en.wikipedia.org): Search for Particle in a box

Free Translation (V = 0) with Boundaries: Particle in a Box (Infinite Square Wall Potential)
A particle of mass m is confined between two walls but free inside.

h 2 d 2 + V ( x ) = E 2 2 m dx

V = 0 for 0 < x < L

V = f for x = 0 and x = L d m The same solution as the free particle but ith different b b t with diff t boundary condition. d diti

( x = 0) = 0 ( x = L) = 0

Final Solution (Energy & Wave function)

n 2h 2 En = 8 mL2 2 n ( x) = L
1/ 2

sin( n x / L )

n = 1,2,3,...

Higher E

Rapidly changing node

quantized zero-point gy energy

Energy, Wave function & Probability density

node

Energy quantized Wave function not constant over x

Quantum (confinement) effect Q t ( fi t) ff t

Classical Limit: Bohrs Correspondence Principle

n by increasing E (~ kT) or m or L

LUMO 375 nm HOMO

1,3,5-hexatriene

LUMO 375 nm HOMO

Coloring of -carotene

Particle in a Finite Box (Potential Well) ( )

(bound state)

Tunneling to classically-forbidden region

Simple Model for Rotational Motion

References
Engel, Ch. 7 g , Molecular Quantum Mechanics, Atkins & Friedman (4th ed. 2005), Ch. 3-4 Introductory Quantum Mechanics, R. L. Liboff (4th ed, 2004), Ch. 7 A Brief Review of Elementary Quantum Chemistry http://vergil.chemistry.gatech.edu/notes/quantrev/quantrev.html g g Wikipedia (http://en.wikipedia.org): Search for Polar coordinate system // Spherical coordinate system Particle on a ring // Particle on a sphere

Particle on a Ring: Free Rotation in 2 Dimension

r0

free particle with boundary condition

Particle on a Ring: Final Solutions

Particle on a Sphere (Rigid Rotor): Rotation in 3D

A particle of mass m free to move anywhere on the 3D surface or a sphere.

Two representations of wave functions p

Angular nodes

Wave functions

Quantum Chemistry in Molecular Modeling: Our Agenda

Postulates, Postulates Schrdinger equation & examples (Ch 2 8) (Ch. 2-8) Computational chemistry (Ch. 16) Hydrogen-like atom (one-electron atom) (Ch. 9) Many-electron atoms (Ch. 10-11) Diatomic molecules (Ch. 12-13) Polyatomic molecules (Ch. 14) P l i l l (Ch Solids

Hydrogen Atom
References
Engel, Ch. 9 Molecular Quantum Mechanics, Atkins & Friedman (4th ed. 2005), Ch.3 Introductory Quantum Mechanics, R. L. Liboff (4th ed, 2004), Ch.10 A Brief Review of Elementary Q y Quantum Chemistry y http://vergil.chemistry.gatech.edu/notes/quantrev/quantrev.html

(2-Body Problem)

H = E K ,electron + E K , nucleus

h2 h2 Ze 2 2 2 +V = e N 2 me 2m N 4 0 r
Electron coordinate Nucleus coordinate

Separation of Internal Motion: Born-Oppenheimer Approximation

Full Schrdinger equation can be separated into two equations: g q p q 1. Atom as a whole through the space; 2. Motion of electron around the nucleus. Electronic structure (1-Body Problem): Forget about nucleus!
h2 2 Ze 2 H = 2 4 0 r 1

1 1 1 + me m N me

in spherical coordinate

Angular part (spherical harmonics)

Radial part (Radial equation)

, n1

Z 2 e 4 En = 2 32 2 e0 h 2 n 2
angular momentum quantum no. magnetic quantum no.
l

with

n = 1, 2,3 ...

principal quantum no.

Rn ,l ( r ) = N n ,l Ln ,l ( ) e / 2 n (Laguerre polynom.) n

Radial Wave Functions Rnl

Designated by three quantum numbers g y q

nlm nl

Energy Levels (Bound States)

4 0 h 2 = me e 2

Ionization Energy gy
Minimum energy required to remove an electron from the ground state g Energy of H atom at ground state (n=1)
4 0 h 2 = me e 2

Z 2 e 4 En = 2 32 2 e0 h 2 n 2

E1 = hcR H

4 He = 2 32 2 e0 h 2

Rydberg Constant

H e4 hcR H = 2 32 2 e0 h 2
I = hcR H

Ionization energy of H atom

Three Quantum Numbers

n: Principal quantum number (n = 1, 2, 3, ) Determines th energies of th electron D t i the i f the l t
Z 2 e 4 En = 2 32 2 e0 h 2 n 2 with n = 1, 2,3 ...

Shells Sh ll

l: Angular momentum quantum number (l = 0, 1, 2, , n1) g q , , , , ) Determines the angular momentum of the electron
Ll =

Subs e s Subshells

{l(l + 1) }1/2 h

(s, p, d f ) with l = 0,1,.., n 1 (s p d, f,)

m: magnetic quantum number (m = 0, 1, 2, , l) g q ( , , , , ) Determines z-component of angular momentum of the electron

Lz, m = m l h with m l = 0, 1, 2,..., l

Shells and Subshells

Shell: n = 1 (K), 2 (L), 3 (M), 4(N), (K) (L) (M) 4(N) Sub-shell (for each n): l = 0 (s), 1 (p), 2 (d), 3(f), 4(g), , n1 m = 0, 1, 2, , l Number of orbitals in the nth shell: n2 (n2 fold degeneracy) Examples : Number of subshells (orbitals) n = 1 : l = 0 only 1s ( ) 1 o y s (1) n = 2 : l = 0, 1 2s (1) , 2p (3) 4 n = 3 : l = 0, 1, 2 3s (1), 3p (3), 3d (5) 9

Z 2 e 4 En = 2 32 2 e0 h 2 n 2

Wave Functions (Atomic Orbitals)

Radial Wave Functions Rnl

1s
node 2 nodes

2s 2p 3s 3p 3d
*Reduced distance

=
Radial node

2 Zr a0

Radial Wave Functions (l = 0, m = 0): s Orbitals

node (radial) d ( di l)

2 nodes

p Orbitals
Radial wave function
2p 3p

node

Angular wave function p orbital (l=1) for n = 2, 3, 4,

d Orbitals
Radial wave function
3d

Angular wave function d orbital (l=2) for n = 3, 4,

Spectroscopic Transitions and Selection Rules p p

Transition (Change of State)
n1, l1,m1 Photon
E = hv

En =

Z e 2 32 2 e0 h 2 n 2
2 4

hcRH

n2, l2,m2

~=R 1 1 H 2 2 n1 n 2

All possible transitions are not permissible. Photon has intrinsic spin angular momentum : s = 1 d orbital (l=2) s orbital (l=0) (X) forbidden (Photon cannot carry away enough angular momentum.)

Selection l f h d S l i rule for hydrogen atom

l = 1

m l = 0, 1

Spectra of Hydrogen Atom (or Hydrogen-Like Atoms)

Balmer, Lyman and Paschen Series (J. Rydberg)
~ = RH 2 2 n 1 n2 1 1

n1 = 1 (Lyman), 2 (Balmer), 3 (Paschen) n2 = n1+1, n1+2, 1 (Rydberg constant) RH = 109667 cm-1 (R db t t)

Electric discharge is passed through gaseous hydrogen. hydrogen H2 molecules and H atoms emit lights of discrete frequencies.