Quantum Mechanics and Probability

Possible Research Topics for PhD Students

Volker Betz

Warwick, 25 January 2011

Quantum Mechanics...

Volker Betz Quantum Mechanics and Probability

 Classical versus Quantum Mechanics
Classical Mechanics
I Particles represented by their position x ∈ R3 and their
momentum p ∈ R3 .
I A particle moving in a potential V is modelled by the equation

1
ẋ(t) = p(t), ṗ(t) = −∇V (x(t)).
m
Quantum Mechanics
I Particles represented by normalized wavefunction ψ ∈ L2 (R3 ).
I No definite position or momentum (uncertainty principle).
But we can determine the probability of finding particles with
certain position or momentum:
Z Z
2 2
Prob(x ∈ A) = |ψ(x)| dx, Prob(p ∈ A) = |ψ(k)|
b dk.
A A
I Dynamics are governed by the Schrödinger equation:
~2
i~∂t ψ(x, t) = Hψ(x, t), H=− ∆+V. H ’Hamiltonian’
2m
Volker Betz Quantum Mechanics and Probability
 Schrödinger equation for a molecule

i~∂t ψ(x, y, t) = Hψ(x, y, t),

with
N Nel
X nuc
~2 X ~2
H=− ∆ xi − ∆y +Vnuc (x)+Vel (y)+Vn,e (x, y)
2mnuc,i 2mel j
i=1 i=j

I Vnuc = Coulomb repulsion between nuclei.

I Vel = Coulomb repulsion between electrons.
I Ve,n = Coulomb attraction between electrons and nuclei.

Volker Betz Quantum Mechanics and Probability

 Schrödinger equation for a molecule

i∂t ψ(x, y, t) = Hψ(x, y, t),

with
N nuc N
el
X 1 X 1
H=− ∆ xi − ∆y + Vnuc (x) + Vel (y) + Vn,e (x, y)
2mnuc,i 2 j
i=1 i=j

I Vnuc = Coulomb repulsion between nuclei.

I Vel = Coulomb repulsion between electrons.
I Ve,n = Coulomb attraction between electrons and nuclei.
I Atomic units: ~ = mel = 1.

Volker Betz Quantum Mechanics and Probability

 Schrödinger equation for a molecule

i∂t ψ(x, y, t) = Hψ(x, y, t),

with
N N
X nuc
ε2 Xel
1
H=− ∆ xi − ∆y + Vnuc (x) + Vel (y) + Vn,e (x, y)
2 2 j
i=1 i=j

I Vnuc = Coulomb repulsion between nuclei.

I Vel = Coulomb repulsion between electrons.
I Ve,n = Coulomb attraction between electrons and nuclei.
I Atomic units: ~ = mel = 1.
I mnuc  mel , for simplicity mnuc,i = ε−2 for all i.

Volker Betz Quantum Mechanics and Probability

 Schrödinger equation for a molecule

iε∂t ψ(x, y, t) = Hψ(x, y, t),

with
N N
X nuc
ε2 Xel
1
H=− ∆ xi − ∆y + Vnuc (x) + Vel (y) + Vn,e (x, y)
2 2 j
i=1 i=j

I Vnuc = Coulomb repulsion between nuclei.

I Vel = Coulomb repulsion between electrons.
I Ve,n = Coulomb attraction between electrons and nuclei.
I Atomic units: ~ = mel = 1.
I mnuc  mel , for simplicity mnuc,i = ε−2 for all i.
I Time change: τ = εt, so ∂t ψ = ε∂τ ψ.

Volker Betz Quantum Mechanics and Probability

 Schrödinger equation for a molecule
 2 
ε
iε∂t ψ(x, y, t) = − ∆x + Hel (x) ψ(x, y, t),
2
with
N N
X nuc
ε2 Xel
1
H=− ∆ xi − ∆y + Vnuc (x) + Vel (y) + Vn,e (x, y)
2 2 j
i=1 i=j

I Vnuc = Coulomb repulsion between nuclei.

I Vel = Coulomb repulsion between electrons.
I Ve,n = Coulomb attraction between electrons and nuclei.
I Atomic units: ~ = mel = 1.
I mnuc  mel , for simplicity mnuc,i = ε−2 for all i.
I Time change: τ = εt, so ∂t ψ = ε∂τ ψ.
I Define electronic Hamiltonian Hel (x) acting in L2 (dy).
Volker Betz Quantum Mechanics and Probability
 The Born-Oppenheimer approximation
 2 
ε
iε∂t ψ(x, y, t) = − ∆x + Hel (x) ψ(x, y, t),
2
I Hel (x) acts on L2 (dy) for all x.
I Idea: The nuclei move slowly, so the electrons stay in their
eigenstates, which depend on the position of the nuclei.

Volker Betz Quantum Mechanics and Probability

 The Born-Oppenheimer approximation
 2 
ε
iε∂t ψ(x, y, t) = − ∆x + Hel (x) ψ(x, y, t),
2
I Hel (x) acts on L2 (dy) for all x.
I Idea: The nuclei move slowly, so the electrons stay in their
eigenstates, which depend on the position of the nuclei.
I Diagonalisation: Let U (x) be the unitary operator on L2 (dy)
that diagonalises Hel (x). Thus
 
E1 (x) 0 ···
U (x)Hel (x)U ∗ (x) =  0 E2 (x) 0 


..
0 0 .

I Ej (x) are the electronic energy bands.

I U (x) and ε2 ∆x do not commute. This couples the energy
bands. But the coupling is small.

Volker Betz Quantum Mechanics and Probability

 The Born-Oppenheimer approximation
 2 
ε
iε∂t ψ(x, y, t) = − ∆x + Hel (x) ψ(x, y, t),
2
I Hel (x) acts on L2 (dy) for all x.
I Idea: The nuclei move slowly, so the electrons stay in their
eigenstates, which depend on the position of the nuclei.
I Diagonalisation: Let U (x) be the unitary operator on L2 (dy)
that diagonalises Hel (x). Thus
 
E1 (x) 0 ···
U (x)Hel (x)U ∗ (x) =  0 E2 (x) 0 


..
0 0 .

I Ej (x) are the electronic energy bands.

I U (x) and ε2 ∆x do not commute. This couples the energy
bands. But the coupling is small.
I Born-Oppenheimer approximation: ignore the coupling!
Volker Betz Quantum Mechanics and Probability
The importance of coupling: Photo-Dissociation of
NaI
Feature Article
I A short laser pulse excites the
electrons from the ground state.
I The nuclei now feel a force due to
the changed electronic configuration
and travel according to the
Born-Oppeneimer approximation.
I At the avoided crossing, the BO
approximation is not very good.
Transitions occur, i.e. some part of
the electronic wave function
switches back to the ground state.
I The part that makes the transitions
is typically very small.

Volker Betz Quantum Mechanics and Probability

Superadiabatic transitions: results and projects
I Determining non-adiabatic transitions quantitatively is an
important open problem in computational chemistry.
I Many approaches are very ad-hoc and justified only by the
fact they work more or less.
I With Benjamin Goddard: we found an expicit formula that
works very well for one-atomic molecules.
I Big challenge: extend this to several nuclear degrees of
freedom.

Volker Betz Quantum Mechanics and Probability

 Superadiabatic transitions: results and projects
I Determining non-adiabatic transitions quantitatively is an
important open problem in computational chemistry.
I Many approaches are very ad-hoc and justified only by the
fact they work more or less.
I With Benjamin Goddard: we found an expicit formula that
works very well for one-atomic molecules.
I Big challenge: extend this to several nuclear degrees of
freedom.
Possible projects
I Extend the theory of superadiabatic transitions (high risk /
high impact).
I Use the techniques developed in some previous work to give
rigorous proofs in many areas of exponential asymptotics
(some progress should be guaranteed).
I Many unsolved intriguing side-issues.
I Mathematical techniques: Asymptotics, complex variables,
PDE, functional analysis.
Volker Betz Quantum Mechanics and Probability
 ... and Probablity

Volker Betz Quantum Mechanics and Probability

 Feynman Path integrals and Feynman-Kac formula
Recall the Schrödinger equation:
1
i∂t ψ(x, t) = Hψ(x, t), H = − ∆ + V. H ’Hamiltonian’
2
It is solved by
 i i
n
e−itH ψ0 = lim e 2n ∆ e n V
n→∞
Z n−1
1 Y i n−1
P 1 2 t
j=0 2t/n |xj+1 −xj | −V (xj+1 ) n
= lim dx j e
n→∞ (2πit/n)n/2
j=1
Z  Z t1 
’=’ exp i |Ẋ(s)|2 − V (X(s)) ds dX
0 2
Classical action integral in the exponent!

Volker Betz Quantum Mechanics and Probability

 Feynman Path integrals and Feynman-Kac formula
Recall the Schrödinger equation:
1
i∂t ψ(x, t) = Hψ(x, t), H = − ∆ + V. H ’Hamiltonian’
2
It is solved by
 i i
n
e−itH ψ0 = lim e 2n ∆ e n V
n→∞
Z n−1
1 Y i n−1
P 1 2 t
j=0 2t/n |xj+1 −xj | −V (xj+1 ) n
= lim dx j e
n→∞ (2πit/n)n/2
j=1
Z  Z t1 
’=’ exp i |Ẋ(s)|2 − V (X(s)) ds dX
0 2
Classical action integral in the exponent!
Unfortunately, this cannot be made into mathematics. But the
’imaginary time version’ can, and is the Feynman-Kac formula:
Z  Z t 
−tH
e ψ0 (x) = exp − V (Xs ) ds dW x (X)
0
Volker Betz Quantum Mechanics and Probability
 Bose-Einstein condensation
Wave function of N indistinguishable particles

Ψ(x1 , . . . , xN ) ∈ L2symm (R3N ),

i.e.
Ψ(x1 , . . . , xN ) = Ψ(xπ(1) , . . . , xπ(N ) ).
Hamiltonian:
N
~2 X X
H=− ∆i + U (xi − xj ) on L2symm (R3N ).
2m
i=1 1 6 i<j 6 N

U is a repulsive pair potential.

Volker Betz Quantum Mechanics and Probability

 Bose-Einstein condensation
Wave function of N indistinguishable particles

Ψ(x1 , . . . , xN ) ∈ L2symm (R3N ),

i.e.
Ψ(x1 , . . . , xN ) = Ψ(xπ(1) , . . . , xπ(N ) ).
Hamiltonian:
N
~2 X X
H=− ∆i + U (xi − xj ) on L2symm (R3N ).
2m
i=1 1 6 i<j 6 N

U is a repulsive pair potential.

One is interested in Tr e−βH , which can be expressed through the
Feynman-Kac formula. But we have to take symmetrisation into
account, which introduces permutations.

Volker Betz Quantum Mechanics and Probability

 Spatial random permutations: finite volume
I Λ ⊂ Rd , finite volmue V .
x = {x1 , . . . , xN } ⊂ Λ ⊂ Rd
I SN = set of permutations on
π : {1, . . . , N } → {1, . . . , N }.
I Typical example for a measure
on SN :

N
!
1 X
Px ({π}) = exp − |xi − xπ(i) |2 .
Y (x)
i=1

Volker Betz Quantum Mechanics and Probability

 Spatial random permutations: finite volume
I Λ ⊂ Rd , finite volmue V .
x = {x1 , . . . , xN } ⊂ Λ ⊂ Rd
I SN = set of permutations on
π : {1, . . . , N } → {1, . . . , N }.
I Typical example for a measure
on SN :

N
!
1 X
Px ({π}) = exp − ξ(xi − xπ(i) ) .
Y (x)
i=1

Volker Betz Quantum Mechanics and Probability

 Spatial random permutations: finite volume
I Λ ⊂ Rd , finite volmue V .
x = {x1 , . . . , xN } ⊂ Λ ⊂ Rd
I SN = set of permutations on
π : {1, . . . , N } → {1, . . . , N }.
I Typical example for a measure
on SN :

N
!
1 X
Px ({π}) = exp − ξ(xi − xπ(i) ) .
Y (x)
i=1
I Aim: Study the infinite volume limit:
N
V, N → ∞, =ρ
V
ρ is the density of points in Λ.

Volker Betz Quantum Mechanics and Probability

 Spatial random permutations: finite volume
I Λ ⊂ Rd , finite volmue V .
x = {x1 , . . . , xN } ⊂ Λ ⊂ Rd
I SN = set of permutations on
π : {1, . . . , N } → {1, . . . , N }.
I Typical example for a measure
on SN :

N
!
1 X
Px ({π}) = exp − ξ(xi − xπ(i) ) .
Y (x)
i=1
I Aim: Study the infinite volume limit:
N
V, N → ∞, =ρ
V
ρ is the density of points in Λ.
I Question: Existence and distribution of infinite cycles.
Volker Betz Quantum Mechanics and Probability
 Macroscopic cycles: heuristics

N
!
1 X
Px ({π}) = exp − ξ(xi − xπ(i) ) .
Y (x)
i=1

I The spatial structure suppresses long jumps.

I For low density ρ long cycles are therefore unlikely.
I Conjecture: there is a phase transition, i.e. infinite cycles only
appear above a critical density ρc .
I Important extension: Pair interaction between jumps. E.g.
jumps are discouraged to cross, or they want to be parallel,
etc...

Volker Betz Quantum Mechanics and Probability

 Spatial random permutations: results and projects
I (with Daniel Ueltschi) In a spatially averaged model we know
that a phase transition exists, also for some form of
interaction.
I We argue non-rigorously that this should have some
implications for BEC.
Projects
I Understand the non-spatially averaged model: Existence of
the infinite volume limit, infinite cycles, decay of correlations...
I Understand the point process associated to the spatially
averaged model: Conjecture: points repel each other.
I Incorporate ’real’ pair interactions into any model.

Methods: Classical probability theory, statistical mechanics.

All of these projects have a (relatively) easy entry point, but are
completely open ended and may get very hard, but also very
rewarding!
Volker Betz Quantum Mechanics and Probability