Quantum Chemistry (CHEM 580, 680, etc.

Tyler J Herman

Notes/Key:
• Definitions in green
• ex) examples and asides in blue
• equations/math in gold

General from 580

• I. Quantum Mechanics is deterministic

ë Properties cannot be uniquely specified
• II. Blackbody Radiation
ë Blackbodies emit and absorb radiation perfectly
ë recall En “ nhν & photoelectric effect
ë Energy is dependent on frequency, not intensity
ë T (kinetic energy): Ttot “ hν ´ φ
• III. Properties of electro-magnetic waves:
2π
ë ypxq “ A cospkxq, k “ λ spatial component
2π
ë yptq “ A cospωtq, ω “ τ temporal component, τ is the period
ë ypx, tq “ A cospkpx ´ ctqq temporal component, c is the speed of the wave

Atomic Structure:

• I. From bohr atom model

ë Emitted light obeys the formula: ∆E “ hν “ RH p n122 ´ 1
n12 q n
2
ă n1
1 2
ë Where RH is the Rydberg constant (RH “ 13.6 eV) and n , n are integer values
ë This results in different “series” of lines depending on the lower limit of n:
ë insert lyman, balmer, paschen, etc. series
ë With R8 “ 1.097 ˆ 107 m´1 for an infinitely-massed nucleus
ë The electron’s acceleration around the nucleus results in EM radiation & a decrease in centrifugal force
ë If the electron collides with the nucleus, this results in a catastrophe!

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• II. De Broglie Model:
ë By Maxwell’s equations of motion and Newton’s laws, we have quantized linear and angular momentum
for these electrons in their “orbits” and their orbital motion is also wavelike:
h
ë λ“ p and momentum is an inverse property to wavelength. (This is the De Broglie wavelength)
ë and any mass + velocity can be converted into a wavelength!
• III. Coulombic Interactions:
Qq BV
ë From Coulomb’s law: F “ 4π0 r 2 using the definition of force as Br
2
e
ë We arrive at V prq “ ´ 4π 0r
with Q “ q “ e pcharge of electronq
ë And each electron has a quantized “orbit” dependent on n:
4n2 ~2 π0
rn “
m e e2

Classical Mechanics:

• I. Newtonian Mechanics
– ex) some particle with position ~r, moving from point 1 to point 2 :
– Motion described by ~rptq
d~
r
– Because velocity is a vectorial property, instantaneous velocity can be described: dt “ ~r9 ptq
– Then, linear momentum: p~ “ m~r9
– From Newton’s 2nd Law: acting force F~ “ d~
p
dt “ p~9 “ m~r:
– So F~x “ m:x “ max , F~y “ m:y “ may , F~z “ m: z “ maz
at each point along a particle’s path of travel, there is a force applied, which exerts work.
ş2
– work (force over distance): w12 “ 1 F~ d~s s is a ’step’ in the trajectory

– if F~ “ m d~
v
dt “ m~ v9 ‰ f ptq (time independent)
ş2 d~v ş2 d~
v m 2 dp~
ş v¨~vq 2
– then w12 “ m 1 dt d~s, with d~s “ ~v dt, w12 “ m 1 dt ~
v dt “ 2 1 dt dt ~v is scalar
ş2
– w12 “ m 2 1 2 1 2
2 1 dpv q “ 2 mv2 ´ 2 mv1 “ T2 ´ T1

– ex) second path from 1 to 2

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– if w12 “ w12 , the system is conservative (a state function)
this also means that F~ ¨ d~s “ 0.
ű

• So, when is a system nonconservative?

ë Through dissipative effects, such as friction
• What is the Born-Oppenheimer Approximation dependent on?
ë Mass of nucleus so much greater than mass of electrons, thus it moves much more
slowly (ą 1000 times) so motions become uncoupled
• II. Conservative Systems

– For a conservative system, D some scalar V that is related to F~ through some gradient function:
F~ “ ´∇V
~ but what is this scalar? Ñ Potential Energy!

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– Since it is a state function, w12 “ V1 ´ V2 “ T2 ´ T1 , so V2 ` T2 “ V1 ` T1 “ Etot

– Goal: find ~rptq given V. Ñ result in 2nd order DiffEQ (and thus requires initial conditions to be known)

´BV
x“
– if ~r is cartesian, m: Bx

– if ~r is spherical, mθ: ‰ ´BV

Bθ r‰
, m: ´BV
Br , etc.

– ex) hydrogen atom, angular momentum

– so let’s use general coordinates to get useful DiffEQs.
– recall ds2 “ dx2 ` dy 2 ` dz 2 (riemann/metric space)
ë but what about how angular momentum changes in time?
– ds2 ‰ dr2 ` dθ2 ` dφ2
– but if we used a generalized coordinate {q}, ds2 “
ř
i,j gij dqi dqj

here g is called a weighting factor or metric tensor, and can describe dx, dy, dz.
but how do we describe gij ?
ÿ Bxl Bxl
gij “ with xl P tx, y, zu
l
Bqi Bqj

note that the metric tensor is related to the jacobian How?

– ex) spherical coordinates
– for this example, gij Ñ grr , so l Ñ x, y, z and qi , qj Ñ r, r
thus
ÿ Bxl Bxl ÿ Bxl Bxl Bx Bx By By Bz Bz
Ñ Ñ ` ` “1
l
Bqi Bqj x,y,z
Br Br Br Br Br Br Br Br

– remember that x “ rsinθcosφ, y “ rsinθsinφ, z “ rcosθ, so:

» fi
1 0 0
g“–0 r2 0 fl
0 0 r2 sin2 θ
ë note off diagonal = 0 (orthogonal system: g = 0)
– which works out well algebraically/trigonometrically, but doesn’t quite add up with matrix work?
– and this is dependent on length being preserved in the system.
– When would the tensor be non-diagonal?
ë for non-orthogonal coordinates!

– So now we have generalized coordinates. what are the coordinates, specifically?

– We seek an equation of motion (EOM) which is valid in any coordinate system.
– there exist constraints on this EOM (walking on the surface of a planet, for example)
– So, to accurately describe a system, we need to build a general equation of motion with
constraints built in.
– ex) static/in equilibrium: F~i “ 0
– F~i “ F~i pappliedq ` f~i pcontraintsq
– imagine some virtual (infinitesimal displacement at dt=0) displacement, δ~r
ë what work occurs during this?

– since F~i “ 0,
ř ~
i Fi δ~
r“0

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• III. Constraints
– 2 main types: Holonomic and non-holonomic
a) Holonomic: some function hp~ri , tq “ 0 (motion on a fixed surface)
b) Non-holonomic: non-rigid.
– If a constraint is holonomic, h=0 and the virtual work due to constraints is zero, i.e. f~i “ 0
– ex) N objects with k constraints

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 Week XII : 27 March

System In a Field

• If we assume no permanent dipole moment in the ground state:

~ |0y “ x1| µ
x0| µ ~ |1y “ 0, x0| µ
~ |1y “ x1| µ
~ |0y “ µ
~T
ˆ ˙ ˆ ˙
µ
~ ¨E~ 0 β “ βσx “ β 0 1
β 0 1 0
• Then the full hamiltonian is:
ˆ ˙ ˆ ˙
0 0 0 cosωt
H“ ´β
0 ~ω0 cosωt 0
So what happens in time??
• We start by making the Rotating Wave Approximation (R.W.A.): i~ dU
dt “ HU
ˆ ˙
0
U “ e´iωt|1yx1| UR with |1y x1| “
1

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