Time Dependent DFT

Runge-Gross Theorem
kinetic external potential
For any system with Hamiltonian of form H = T + W + Vext ,
e-e interaction

Runge & Gross (1984) proved the 1-1 mapping:


n(r t) vext(r t)

 For a given initial-state  , the time-evolving one-body density n(r t) tells you
everything about the time-evolving interacting electronic system, exactly.

This follows from :

0, n(r,t)  unique vext(r,t)  H(t)  (t)  all observables

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 Examples

spectra of chiral fullerenes: D2C84

F. Furche and R. Ahlrichs, JACS 124, 3804 (2002). GS and EES geometries of diphenyl-
acetylene
240 optically allowed transitions were required
to simulate the spectrum

GS and EES dipole moments for the

DPP dye.
 Proof of the Runge-Gross Theorem (1/4)

Consider two systems of N interacting electrons, both starting in the same 0 ,

but evolving under different potentials vext(r,t) and vext’(r,t) respectively:

A purely time-dependent function

vext(t), (t)


vext’(t), ’(t)
Assume Taylor-
expandability:

RG prove that the resulting densities n(r,t) and n’(r,t) eventually must differ,
i.e.

same

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 Proof of the Runge-Gross Theorem (2/4)

The first part of the proof shows that the current-densities must differ.
Consider Heisenberg e.o.m’s for the current-density in each system,

the part of H that

differs in the two
systems

;t )

At the initial time:

initial density
 if initially the 2 potentials differ, then j and j’ differ infinitesimally later ☺
Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008
 Proof of the Runge-Gross Theorem (3/4)

If vext(r,0) = v’ext(r,0), then look at later times by repeatedly using Heisenberg e.o.m :

… *

As vext(r,t) – v’ext(r,t) = c(t), and assuming potentials are Taylor-expandable at

t=0, there must be some k for which RHS = 0 

1-1
 proves j(r,t) vext(r,t) 1st part of RG ☺


The second part of RG proves 1-1 between densities and potentials:

Take div. of both sides of * and use the eqn of continuity, …

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 Proof of the Runge-Gross Theorem (4/4)

≡ u(r) is nonzero for some k, but must

taking the div here be nonzero?
Yes!
By reductio ad absurdum: assume

Then assume fall-off of n0 rapid enough that

surface-integral  0

integrand 0, so if integral 0, then u  0  contradiction

i.e. sam
e

1-1 mapping between time-dependent densities and potentials, for a

given initial state
 Adiabatic approximation

n r, t 
VH  r , t    d r  3 depends on density at time t
r - r (instantaneous, no memory)

Vxc  n r, t  is a functional of n r, t  , t   t

The time-dependent xc potential has a memory!

Adiabatic approximation: V adia

xc  n r, t   V  n(t ) r 
gs
xc

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 TDKS scheme: 3 Steps

1
 r ,0 
Prepare the initial state, usually the ground state, by
a static DFT calculation. This gives the initial orbitals:  (0)
j

2 Solve TDKS equations selfconsistently, using an approximate

time-dependent xc potential which matches the static one used
in step 1. This gives the TDKS orbitals:
j   r , t   n r , t 

3 Calculate the relevant observable(s) as a functional of n r , t 

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 Time-dependent selfconsistency (1)

start with
propagate
selfconsistent
until here
KS ground state

t0 T
time

I. Propagate
 2
 old

i j   2  VKS  t   j , t   t0 , T 

n t     j  t 
2
II. With the density calculate the new KS potential
j

V new
KS  t   Vext  t   VH  n t    Vxc  n t   for all t   t0 , T 

III. Selfconsistency is reached if V old

KS t  V t ,
new
KS t   t0 , T 
Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008
 Example: two electrons on a 2D quantum strip

initial-state density
hard walls
periodic exact
boundaries
(travelling LDA
waves)
z
x (standing waves)

Charge-density oscillations
● Initial state: constant electric field,
which is suddenly switched off

Δ ● After switch-off, free propagation of

the charge-density oscillations

C.A. Ullrich, J. Chem. Phys. 125, 234108 (2006)

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 Construction of the exact xc potential

Step 1: solve full 2-electron Schrödinger equation

   2 2
1   
   1
 V  z1 ,t   V  z 2 ,t      i    r1 , r2 ,t   0
2

 2 2 r1  r2 t 

Step 2: calculate the exact time-dependent density

  2
  dr2   r , r2 ,t   n z ,t   2   z ,t 
2

s1 ,s 2

Step 3: find that TDKS system which reproduces the density

 1 d2 
   V  z ,t   VH  z ,t   Vxc  z ,t   i    z ,t   0
 2 dz
2
t 
Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008
 Construction of the exact xc potential


 n r , t  
Ansatz:  r ,t  exp i  r , t  
2
A
   V
Vxc  r ,t    V  r ,t   VH  r ,t 
xc

1 2  1   2
  ln n r ,t    ln n r ,t 
4 8
 1   2
   r ,t      r ,t 
2
dyn
V xc
Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008
 2D quantum strip: charge-density oscillations

density
adiabatic Vxc
exact Vxc

● The TD xc potential can be constructed from a TD density

● Adiabatic approximations get most of the qualitative behavior right,
but there are clear indications of nonadiabatic (memory) effects.

Adapted from C. Ullrich and N. Maitra. APS March Meeting 2008

 TDDFT in linear response

Poles at true Poles at KS

excitations excitations

adiabatic approx: no -dep

Need (1) ground-state vS,0[n0](r), and its bare excitations

(2) XC kernel
Yields exact spectra in principle; in
practice, approxs needed in (1) and (2).
Petersilka, Gossmann, Gross, (PRL, 1996)
 Matrix equations (Casida’s equations)

Quantum chemistry codes cast eqns into a matrix of coupled KS single

excitations (Casida 1996) : Diagonalize

q = (i  a)

 Excitation energies and oscillator strengths

Transitions for
the Helium atom