Chemistry 341 Physical Chemistry I Fall 2011

EXAM 1 REVIEW SHEET [Exam 1: Friday September30, 11:10 AM–12:00 PM, Packard Lab Aud. 101] Quantum Mechanics
1. Wave theory of light • constructive interference • destructive interference Planck quantum theory • blackbody radiation hν 8π ν 2 ρ( ν ) = ⋅ hν 3 c ⎧ kT ⎫ ⎨ e − 1⎬ ⎩ ⎭ • average energy of an oscillator

2.

ε=
3.

hν ⎧ ⎨e ⎩
hν kT

⎫ − 1⎬ ⎭

Photoelectric effect 1 • k . e. = me v 2 = hν − φ 2 de Broglie relation λ = Wave behavior in 1-D • • wavelength ( λ ) period ( τ )
~ wavenumber ( ν = 1

4. 5.

h p

λ

)

frequency ( ν =

1

τ

)

6.

Differential equation for the spatial dependence of a standing wave 2 d2 ⎛ 2π ⎞ D = −⎜ ⎟ D ⎝ λ ⎠ dx 2 Schrödinger equation in 1-D
− h2 d 2 ψ + Vψ = Eψ 2m dx 2

7.

Eigenvalue problem $ Λ ψ = λψ $ ψ is an eigenfunction of the operator Λ with eigenvalue λ 9. ⎛ nπ x⎞ ⎛ 2⎞ ψ n = ⎜ ⎟ sin⎜ ⎟ with n=1.. 2. 3. 12. … ⎝ 2⎠ h2 n2 • En = with n=1. 2. electronic spectra of polyenes CNHN+2 … prediction of lowest energy p-electron transition Quantum mechanical tunneling through barrier of height Vo and width a … light mass particles can tunnel into regions where E<Vo ⎡ {eκa − e −κa }2 ⎤ T=⎢ + 1⎥ ( ) ⎢ ⎥ ⎣ 16 ε 1 − ε ⎦ 1/ 2 o −1 {2 mV (1 − ε )} with κ = h and ε = E Vo . … ⎝ a⎠ ⎝ a ⎠ probability of finding a particle between x1 and x2 x2 2 ∫ x = x1 ψ n dx 1/ 2 10. 3. . 3. 2. Heisenberg uncertainty principle h ∆x ∆p ≥ 2 Three postulates concerning quantum theory Average value theorem $ ∫ ψ * Λ ψ dv λ = ∫ ψ * ψ dv Quantum mechanical operators $ • x⇒ x h ∂ ∂ $ px ⇒ = −i h • ∂x i ∂x Particle in a 1-D box • condition for a standing wave in a 1-D box of length a ⎛ λ⎞ a = n⎜ ⎟ with n=1. 11.. 8 ma 2 • • • 14. 13.8.

n y = with nx = 1. … ⎨ + 8 m ⎩ a 2 b2 c2 ⎭ • Particle in 3-D cubic box of sides a – idea of degenerate levels h2 2 E n x . 1 ⎛ k⎞ with νo = ⎜ ⎟ 2π ⎝ µ ⎠ ψ v … the number of nodes ( ↑ ) as the energy E v goes ( ↑ ) Particle of mass m on a circle on a circle of radius R [also rigid rotor in 2-D where m= µ] • • En = h 2 ml2 with ml = 0. …. …. ±1. 2.n y = ⎨ + ⎬ with nx = 1. 2. 2. 2. ny = 1. … 8 ma 2 x { } 17. 2. … 2 nx + n y 8 ma { } 16.n y .n z = + ⎬ with nx = 1. … and ny = 1. … • 18. 2. 1. … and nz = 1.n z = n 2 + ny + nz2 with nx = 1. … 8 m ⎩ a 2 b2 ⎭ • Particle in 2-D square box of sides a – idea of degenerate levels h2 2 2 E n x . ±2.15. … and nz = 1. … 8π 2 m R 2 1/ 2 • ⎛ 1 ⎞ ψ ml = ⎜ ⎟ e i ml φ ⎝ 2π ⎠ with ml > 0 counterclockwise rotation looking down on circle (clockwise rotation looking along positive-z axis) and ml < 0 clockwise rotation looking down on circle (counterclockwise rotation looking along positive z-axis) benzene and porphine group as examples . Schrödinger equation in 2-D • Particle in 2-D box of dimensions a x b 2 2 h 2 ⎧ nx n y ⎫ E n x .n y . Schrödinger equation in 3-D • Particle in 3-D box of dimensions a x b x c 2 2 h 2 ⎧ nx ny nz2 ⎫ E n x . Harmonic oscillator 1 • V ( x) = k x 2 2 1⎞ ⎛ • Ev = ⎜ v + ⎟ h νo ⎝ 2⎠ 1/ 2 with v =0. 2. 2. … and ny = 1. 2. ny = 1. 2. 2.

) 2I h where B = 8π 2 c I m $ m L2 Yl l = l ( l + 1) h 2 Yl l with ( l = 0.. ±2. .. …) z l l l • • l . 2 ..19. 1. 2.) ml ml $ L Y = m hY with ( m = 0. ±1. Rigid rotor in 3D • Diatomic molecule I = µ R 2 • h2 E J = J ( J + 1) = B h c J ( J + 1) with ( J = 0. 1..