The laser driven hydrogen atom.

Ciaran McCormick
Queens University Belfast
March 28th, 2012
Ciaran McCormick (Queens University Belfast) March 28th, 2012 1 / 16
Recap 1
The Time Dependent Sch¨odinger Equation
i
∂Ψ
∂t
= HΨ
The Time Dependent Hamiltonian
H = −
1
2

2

1
r

i
c
A
z
(t)

∂z
Wavefunction
Ψ(r, t) =

=0
f

(r , t)
r
Y
,m
(θ, φ)
Ciaran McCormick (Queens University Belfast) March 28th, 2012 2 / 16
Recap 2
TDSE
i

∂t

=0
1
r
f

(r , t)Y
,0
(θ, φ) = H

=0
1
r
f

(r , t)Y
,0
(θ, φ)
Orthogonality and Spherical Harmonics
_

0

_
π
0
dθ sin θ Y

,m
(θ, φ)Y

,m
(θ, φ) = δ
,
δ
m,m

TDSE depending only on radial distance and time
i

∂t
f

(r , t)
r
=

=0
_
Y

,0
(θ, φ)H
f

(r , t)
r
Y
,0
(θ, φ) dΩ
Ciaran McCormick (Queens University Belfast) March 28th, 2012 3 / 16
Recap 3
Laplacian Operator

2
=
1
r
2

∂r
_
r
2

∂r
_
+
1
r
2
_
1
sin θ

∂θ
_
sin θ

∂θ
_
+
1
sin
2
θ

2
∂φ
2
_
Spherical Harmonic Eigenvalue Equation

_
1
sin θ

∂θ
_
sin θ

∂θ
_
+
1
sin
2
θ

2
∂φ
2
_
Y
,0
(θ, φ) = ( + 1)Y
,0
(θ, φ)
TDSE
i
r

∂t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

r

i
c
A
z
(t)

_
Y

,0
(θ, φ)

∂z
_
Y
,0
(θ, φ)
f

r
_
dΩ
Ciaran McCormick (Queens University Belfast) March 28th, 2012 4 / 16
Recap 3
Laplacian Operator

2
=
1
r
2

∂r
_
r
2

∂r
_
+
1
r
2
_
1
sin θ

∂θ
_
sin θ

∂θ
_
+
1
sin
2
θ

2
∂φ
2
_
Spherical Harmonic Eigenvalue Equation

_
1
sin θ

∂θ
_
sin θ

∂θ
_
+
1
sin
2
θ

2
∂φ
2
_
Y
,0
(θ, φ) = ( + 1)Y
,0
(θ, φ)
TDSE
i
r

∂t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

r

i
c
A
z
(t)

_
Y

,0
(θ, φ)

∂z
_
Y
,0
(θ, φ)
f

r
_
dΩ
Ciaran McCormick (Queens University Belfast) March 28th, 2012 4 / 16
Recap 3
Laplacian Operator

2
=
1
r
2

∂r
_
r
2

∂r
_
+
1
r
2
_
1
sin θ

∂θ
_
sin θ

∂θ
_
+
1
sin
2
θ

2
∂φ
2
_
Spherical Harmonic Eigenvalue Equation

_
1
sin θ

∂θ
_
sin θ

∂θ
_
+
1
sin
2
θ

2
∂φ
2
_
Y
,0
(θ, φ) = ( + 1)Y
,0
(θ, φ)
TDSE
i
r

∂t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

r
Ciaran McCormick (Queens University Belfast) March 28th, 2012 4 / 16
Recap 4: TDSE
TDSE - No laser field
i

∂t
f

(r , t) =
_

1
2
d
2
dr
2
+
( + 1)
2r
2

1
r
_
f

(r , t)
Separation of Variables
f

(r , t) = g

(r )T

(t)
Radial Dependent Part
_

1
2
d
2
dr
2
+
( + 1)
r
2

1
r
_
g

(r ) = E g

(r )
Time Dependent Part
dT
dt
= −iET(t)
T = e
−iEt
Ciaran McCormick (Queens University Belfast) March 28th, 2012 5 / 16
Recap 5: Time Independent Sch¨odinger Equation
Eigenvalue Problem
Finite Difference Equation
d
2
dr
2
(f

(r , t)) =
f

(r + δr , t) −2f

(r , t) + f

(r −δr , t)
(δr )
2
where the red blocks are,

1
2(δr )
2
and the black blocks are given by
( + 1)
r
2

1
r
+
1
(δr )
2
Ciaran McCormick (Queens University Belfast) March 28th, 2012 6 / 16
Some Results
N = 999, b = 50.0au and E is in atomic units
l

E
estimate
E
actual
0 -0.499687890015716 -0.5
1 -0.125006512903812 -0.125
2 -5.555581160715379E-002 -5.555555596947670E-002
3 -3.124571705439556E-002 -3.125000000000000E-002
4 -1.977527744935510E-002 -1.999999955296516E-002
5 -1.242637199326190E-002 -1.388888899236917E-002
6 -6.147446767590584E-003 -1.020408142358065E-002
7 -1.577378457009712E-005 -7.812500000000000E-003
8 6.274400917348134E-003 -6.172839552164078E-003
9 1.284838845282180E-002 -4.999999888241291E-003
10 1.976679202690924E-002 -4.132231231778860E-003
Ciaran McCormick (Queens University Belfast) March 28th, 2012 7 / 16
Time Dependent Schr¨ odinger Equation
TDSE
i

∂t
Ψ(r, t) = HΨ(r, t)
TDSE
i
r

∂t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

r

i
c
A
z
(t)

=0
_
Y

,0
(θ, φ)

∂z
_
Y
,0
(θ, φ)
f

r
_
dΩ
Ciaran McCormick (Queens University Belfast) March 28th, 2012 8 / 16
Time Dependent Schr¨ odinger Equation
Partial Derivative

∂z
= cos θ

∂r

sin θ
r

∂θ
Inserting the partial derivative
i
c
A
z
(t)

=0
__
Y

,0
sin θ
d

(Y
,0
(θ, φ)) dΩ
_
f

(r , t)
r
2

i
c
A
z
(t)

=0
__
Y

,0
(θ, φ) cos θ Y
,0
(θ, φ) dΩ
_

∂r
_
f

(r , t)
r
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 9 / 16
Final TDSE
i

∂t
f

(r , t) =
_

1
2
d
2
dr
2
+
( + 1)
2r
2

1
r
_
f

(r , t)
+
i
c
A
z
(t)
_

_
(2 + 1)(2 −1)
_

r


∂r
_
f
−1
(r , t)

( + 1)
_
(2 + 1)(2 + 3)
_
( + 1)
r
+

∂r
_
f
+1
(r , t)
_
Finite Difference Equation, First Derivative
d
dr
(f

(r , t)) =
f

(r + δr , t) −f

(r −δr , t)
2δr
Finite Difference Equation, Second Derivative
d
2
dr
2
(f

(r , t)) =
f

(r + δr , t) −f

(r , t) + f

(r −δr , t)
(δr )
2
Ciaran McCormick (Queens University Belfast) March 28th, 2012 10 / 16
Diagrammatic Representation
Algebraic Eigenvalue Problem
Black Diagonal
( + 1)
2r
2

1
r
+
1
(δr )
2
Blue Diagonals

1
2
_
1
(δr )
2
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 11 / 16
Diagrammatic Representation
Eigenvalue-Eigenvector Problem
+ 1,r Red Supra-Diagonal

i
c
A
z
(t)
_
( + 1)
2
r
_
(2 + 1)(2 + 3)
_
−1,r Red Sub-Diagonal
i
c
A
z
(t)
_

2
r
_
(2 + 1)(2 −1)
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 12 / 16
Diagrammatic Representation
Algebraic Eigenvalue Problem
+ 1, r+1 Green Supra-Diagonal

i
c
A
z
(t)
_
( + 1)
2δr
_
(2 + 1)(2 + 3)
_
−1, r-1 Green Sub-Block
i
c
A
z
(t)
_

2δr
_
(2 + 1)(2 −1)
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 13 / 16
Diagrammatic Representation
Algebraic Eigenvalue Problem
−1, r+1 Purple Supra-Block

i
c
A
z
(t)
_

2δr
_
(2 + 1)(2 −1)
_
+ 1, r-1 Purple Sub-Diagonal
i
c
A
z
(t)
_
( + 1)
2δr
_
(2 + 1)(2 + 3)
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 14 / 16
Time Propagation
TDSE
i
˙
Ψ = HΨ
Taylor Series Expansion
Ψ(t + ∆t) = Ψ(t) + ∆t
˙
Ψ(t) +
(∆t)
2
2!
¨
Ψ(t) + . . .
From the TDSE we can see that
˙
Ψ(t) =
H(t)Ψ(t)
i
Differentiating with respect to t
¨
Ψ(t) =
˙
H(t)Ψ(t) + H(t)
˙
Ψ(t)
i

H(t)
˙
Ψ(t)
i
Ciaran McCormick (Queens University Belfast) March 28th, 2012 15 / 16
Time Propagation 2
Substituting in the expression for the first derivative
¨
Ψ(t) ≈
H
2
(t)Ψ(t)
i
The third derivative can be found similarly
...
Ψ
(t) ≈
H
3
(t)Ψ(t)
i
3
Time Propagator
Ψ(t+∆t) ≈ Ψ(t)+
∆tH(t)Ψ(t)
i
+
(∆t)
2
H
2
(t)Ψ(t)
i
2
2!
+· · ·+
(∆t)
n
H
n
(t)Ψ(t)
i
n
n!
Ciaran McCormick (Queens University Belfast) March 28th, 2012 16 / 16

t) = =0 f (r . φ) Ciaran McCormick (Queens University Belfast) March 28th.m (θ. 2012 2 / 16 .Recap 1 The Time Dependent Sch¨dinger Equation o i ∂Ψ = HΨ ∂t The Time Dependent Hamiltonian H=− 1 2 2 − 1 i ∂ − Az (t) r c ∂z Wavefunction ∞ Ψ(r. t) Y r .

φ) r Orthogonality and Spherical Harmonics 2π π dφ 0 0 dθ sin θ Y ∗ (θ. φ) = H r ∞ =0 1 f (r . 2012 3 / 16 . φ)H =0 f (r .Recap 2 TDSE ∂ i ∂t ∞ =0 1 f (r . φ) dΩ r Ciaran McCormick (Queens University Belfast) March 28th. t)Y . φ) = δ . t) i = ∂t r ∞ Y ∗. δm. φ)Y . t)Y .0 (θ.0 (θ.m TDSE depending only on radial distance and time ∂ f (r . t) Y .0 (θ.m (θ.0 (θ.m .

φ) = ( + 1)Y .0 (θ. φ) f r dΩ March 28th. φ) TDSE i ∂ f r ∂t = − ( + 1) f 1f 1f − − 2 2r r 2 r r r i Az (t) c ∞ Y ∗.0 (θ.Recap 3 Laplacian Operator 2 = 1 ∂ r 2 ∂r r2 ∂ ∂r + 1 r2 1 ∂ sin θ ∂θ sin θ ∂ ∂θ + 1 ∂2 sin2 θ ∂φ2 Spherical Harmonic Eigenvalue Equation − 1 ∂ sin θ ∂θ sin θ ∂ ∂θ + 1 ∂2 sin2 θ ∂φ2 Y . φ) ∂ ∂z Y .0 (θ.0 (θ. 2012 4 / 16 Ciaran McCormick (Queens University Belfast) .

Recap 3 Laplacian Operator 2 = 1 ∂ r 2 ∂r r2 ∂ ∂r + 1 r2 1 ∂ sin θ ∂θ sin θ ∂ ∂θ + 1 ∂2 sin2 θ ∂φ2 Spherical Harmonic Eigenvalue Equation − 1 ∂ sin θ ∂θ sin θ ∂ ∂θ + 1 ∂2 sin2 θ ∂φ2 Y .0 (θ. φ) = ( + 1)Y .0 (θ.0 (θ. φ) TDSE i ∂ f r ∂t = − ( + 1) f 1f 1f − − 2 2r r 2 r r r i Az (t) c ∞ Y ∗. φ) ∂ ∂z Y .0 (θ. 2012 4 / 16 Ciaran McCormick (Queens University Belfast) . φ) f r dΩ March 28th.

φ) TDSE i ∂ f r ∂t = ( + 1) f 1f 1f − − 2 2r r 2 r r r Ciaran McCormick (Queens University Belfast) March 28th.0 (θ.Recap 3 Laplacian Operator 2 = 1 ∂ r 2 ∂r r2 ∂ ∂r + 1 r2 1 ∂ sin θ ∂θ sin θ ∂ ∂θ + 1 ∂2 sin2 θ ∂φ2 Spherical Harmonic Eigenvalue Equation − 1 ∂ sin θ ∂θ sin θ ∂ ∂θ + 1 ∂2 sin2 θ ∂φ2 Y . φ) = ( + 1)Y . 2012 4 / 16 .0 (θ.

t) = ∂t − 1 d2 ( + 1) 1 + − 2 2 dr 2r 2 r f (r . t) Separation of Variables f (r . 2012 5 / 16 .No laser field i ∂ f (r .Recap 4: TDSE TDSE . t) = g (r )T (t) Radial Dependent Part 1 d2 ( + 1) 1 − + − 2 2 dr r2 r g (r ) = E g (r ) Time Dependent Part dT = −iET (t) dt T = e −iEt Ciaran McCormick (Queens University Belfast) March 28th.

2012 6 / 16 1 2(δr )2 . t) + f (r − δr . t) (δr )2 where the red blocks are. t)) = dr 2 f (r + δr . t) − 2f (r . − and the black blocks are given by ( + 1) 1 1 − + r2 r (δr )2 Ciaran McCormick (Queens University Belfast) March 28th.Recap 5: Time Independent Sch¨dinger Equation o Eigenvalue Problem Finite Difference Equation d2 (f (r .

999999888241291E-003 -4.124571705439556E-002 -1. b = 50. 2012 7 / 16 .812500000000000E-003 -6.132231231778860E-003 Ciaran McCormick (Queens University Belfast) March 28th.977527744935510E-002 -1.5 -0.284838845282180E-002 1.125 -5.Some Results N = 999.172839552164078E-003 -4.0au and E is in atomic units l 0 1 2 3 4 5 6 7 8 9 10 Eestimate -0.147446767590584E-003 -1.125000000000000E-002 -1.499687890015716 -0.555555596947670E-002 -3.577378457009712E-005 6.242637199326190E-002 -6.976679202690924E-002 Eactual -0.125006512903812 -5.388888899236917E-002 -1.020408142358065E-002 -7.999999955296516E-002 -1.555581160715379E-002 -3.274400917348134E-003 1.

Time Dependent Schr¨dinger Equation o TDSE i ∂ Ψ(r. t) = HΨ(r. 2012 8 / 16 . φ) f r dΩ Ciaran McCormick (Queens University Belfast) March 28th. φ) =0 ∂ ∂z Y . t) ∂t TDSE i ∂ f r ∂t = − ( + 1) f 1f 1f − − 2 2r r 2 r r r i Az (t) c ∞ Y ∗.0 (θ.0 (θ.

φ) cos θ Y .Time Dependent Schr¨dinger Equation o Partial Derivative ∂ sin θ ∂ ∂ = cos θ − ∂z ∂r r ∂θ Inserting the partial derivative i Az (t) c − i Az (t) c ∞ Y ∗.0 (θ. φ)) dΩ dθ f (r .0 sin θ =0 ∞ d (Y . 2012 9 / 16 .0 (θ. φ) dΩ =0 Ciaran McCormick (Queens University Belfast) March 28th. t) r2 ∂ ∂r f (r . t) r Y ∗.0 (θ.

t) i Az (t) c (2 + 1)(2 − 1) r ( + 1) (2 + 1)(2 + 3) ( + 1) ∂ + r ∂r +1 (r . t)) = dr 2δr Finite Difference Equation. t) − f (r − δr . t) Finite Difference Equation. Second Derivative d2 f (r + δr . t) d (f (r . t) + f (r − δr .Final TDSE i ∂ f (r . First Derivative f (r + δr . t)) = dr 2 (δr )2 Ciaran McCormick (Queens University Belfast) March 28th. t) (f (r . t) = ∂t + − − 1 d2 ( + 1) 1 + − 2 2 dr 2r 2 r f (r . t) − f (r . t) − ∂ ∂r f f −1 (r . 2012 10 / 16 .

2012 11 / 16 .Diagrammatic Representation Algebraic Eigenvalue Problem Black Diagonal ( + 1) 1 1 − + 2r 2 r (δr )2 Ciaran McCormick (Queens University Belfast) Blue Diagonals − 1 2 1 (δr )2 March 28th.

r Red Supra-Diagonal i − Az (t) c r ( + 1)2 (2 + 1)(2 + 3) − 1.Diagrammatic Representation Eigenvalue-Eigenvector Problem + 1. 2012 12 / 16 Ciaran McCormick (Queens University Belfast) .r Red Sub-Diagonal i Az (t) c r 2 (2 + 1)(2 − 1) March 28th.

r+1 Green Supra-Diagonal i − Az (t) c 2δr ( + 1) (2 + 1)(2 + 3) − 1. 2012 13 / 16 Ciaran McCormick (Queens University Belfast) . r-1 Green Sub-Block i Az (t) c 2δr (2 + 1)(2 − 1) March 28th.Diagrammatic Representation Algebraic Eigenvalue Problem + 1.

r+1 Purple Supra-Block i − Az (t) c 2δr + 1.Diagrammatic Representation Algebraic Eigenvalue Problem − 1. 2012 14 / 16 (2 + 1)(2 − 1) Ciaran McCormick (Queens University Belfast) . r-1 Purple Sub-Diagonal i Az (t) c 2δr ( + 1) (2 + 1)(2 + 3) March 28th.

Time Propagation TDSE ˙ iΨ = HΨ Taylor Series Expansion (∆t)2 ¨ ˙ Ψ(t + ∆t) = Ψ(t) + ∆t Ψ(t) + Ψ(t) + . . 2! From the TDSE we can see that H(t)Ψ(t) ˙ Ψ(t) = i Differentiating with respect to t ˙ ˙ ˙ H(t)Ψ(t) H(t)Ψ(t) + H(t)Ψ(t) ¨ Ψ(t) = ≈ i i Ciaran McCormick (Queens University Belfast) March 28th. . 2012 15 / 16 .

H 3 (t)Ψ(t) (t) ≈ Ψ i3 Time Propagator Ψ(t+∆t) ≈ Ψ(t)+ ∆tH(t)Ψ(t) (∆t)2 H 2 (t)Ψ(t) (∆t)n H n (t)Ψ(t) + +· · ·+ 2 i in n! i 2! Ciaran McCormick (Queens University Belfast) March 28th.Time Propagation 2 Substituting in the expression for the first derivative H 2 (t)Ψ(t) ¨ Ψ(t) ≈ i The third derivative can be found similarly .. 2012 16 / 16 ..

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