Time-dependent density-functional theory

Carsten A. Ullrich Neepa T. Maitra

University of Missouri-Columbia Hunter College, CUNY

APS March Meeting 2008, New Orleans

 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

 1. Survey Time-dependent Schrödinger equation


 
i  (r1 ,..., rN , t )  Tˆ  Vˆ (t )  Wˆ  (r1 ,..., rN , t )
t
2
kinetic energy N  2 2
electron 1
Wˆ  
N
e
Tˆ   
j
operator: interaction:
2m 2 j ,k r j  rk
j 1 j k

The TDSE describes the time evolution of a many-body state  t  ,

starting from an initial state   t0  , under the influence of an
Vˆ  t    V  r j , t  .
N
external time-dependent potential
j 1

From now on, we’ll (mostly) use atomic units (e = m = h = 1).

1. Survey Real-time electron dynamics: first scenario

Start from nonequilibrium initial state, evolve in static potential:

t=0 t>0

Charge-density oscillations in metallic

clusters or nanoparticles (plasmonics)

New J. Chem. 30, 1121 (2006)

Nature Mat. Vol. 2 No. 4 (2003)
1. Survey Real-time electron dynamics: second scenario

Start from ground state, evolve in time-dependent driving field:

t=0 t>0

Nonlinear response and ionization of atoms

and molecules in strong laser fields
1. Survey Coupled electron-nuclear dynamics

● Dissociation of molecules (laser or collision induced)

● Coulomb explosion of clusters
● Chemical reactions

High-energy proton hitting ethene

T. Burnus, M.A.L. Marques, E.K.U. Gross,

Phys. Rev. A 71, 010501(R) (2005)

Nuclear dynamics
treated classically

For a quantum treatment of nuclear dynamics within TDDFT (beyond the

scope of this tutorial), see O. Butriy et al., Phys. Rev. A 76, 052514 (2007).
1. Survey Linear response

tickle the system

observe how the
system responds
(r, t ) at a later time

(r, t )

n1 (r, t )   dr dt    r, t , r, t  V1  r, t 

density density-density perturbation
response response function
 1. Survey Optical spectroscopy

● Uses weak CW laser as Probe

Green
● System Response has peaks at fluorescent
protein
electronic excitation energies
Photoabsorption cross section

Na2 Na4

Theory

Energy (eV)
Vasiliev et al., PRB 65, 115416 (2002)
Marques et al., PRL 90, 258101 (2003)
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

 2. Fundamentals 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
 2. Fundamentals 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:

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
 2. Fundamentals 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 ☺
 2. Fundamentals 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, …

 2. Fundamentals 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. same

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

given initial state
 2. Fundamentals The TDKS system

n v for given 0, implies any observable is a functional of n and 0

-- So map interacting system to a non-interacting (Kohn-Sham) one, that
reproduces the same n(r,t).
All properties of the true system can be extracted from TDKS  “bigger-faster-
cheaper” calculations of spectra and dynamics
KS “electrons” evolve in the 1-body KS potential:

functional of the history of the density

and the initial states

-- memory-dependence (see more shortly!)

If begin in ground-state, then no initial-state dependence, since by HK,

 2. Fundamentals Clarifications and Extensions

But how do we know a non-interacting system exists that reproduces a given

interacting evolution n(r,t) ?

 van Leeuwen (PRL, 1999)

(under mild restrictions of the choice of the KS initial state0)

The KS potential is not the density-functional derivative of any action !

If it were, causality would be violated:

Vxc[n,0,0](r,t) must be causal – i.e. cannot depend on n(r t’>t)

But if then

But RHS must be symmetric in (t,t’)  symmetry-causality paradox.

van Leeuwen (PRL 1998) showed how an action, and variational principle, may be
defined, using Keldysh contours.
2. Fundamentals Clarifications and Extensions

Restriction to Taylor-expandable potentials means RG is technically not valid

for many potentials, eg adiabatic turn-on, although RG is assumed in practise.

van Leeuwen (Int. J. Mod. Phys. B. 2001) extended the RG proof in the linear
response regime to the wider class of Laplace-transformable potentials.

The first step of the RG proof showed a 1-1 mapping between currents and
potentials  TD current-density FT

In principle, must use TDCDFT (not TDDFT) for

-- response of periodic systems (solids) in uniform E-fields

-- in presence of external magnetic fields

(Maitra, Souza, Burke, PRB 2003; Ghosh & Dhara, PRA, 1988)

In practice, approximate functionals of current are simpler where spatial non-

local dependence is important
(Vignale & Kohn, 1996; Vignale, Ullrich & Conti 1997) … Stay tuned!
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

 3. TDKS Time-dependent Kohn-Sham scheme (1)

Consider an N-electron system, starting from a stationary state.

Solve a set of static KS equations to get a set of N ground-state orbitals:

 2  (0)
   Vext  r,t0   VH  r   Vxc  r   j  r    j (j 0)  r 
 2 

The N static KS orbitals are taken as initial orbitals and will be propagated in time:

 (0)
j  r    j  r, t0  , j  1,..., N

  2 
i  j  r, t      Vext  r, t   VH  r, t   Vxc  r, t   j  r, t 
t  2 
N
n r , t     j  r , t 
2
Time-dependent density:
j 1
3. TDKS Time-dependent Kohn-Sham scheme (2)

Only the N initially occupied orbitals are propagated. How can this be sufficient
to describe all possible excitation processes?? Here’s a simple argument:

Expand TDKS orbitals in complete basis of static KS orbitals,


 j  r, t    a jk  t   ( 0)
k r
k 1

finite for kN

A time-dependent potential causes the TDKS orbitals to acquire admixtures of

initially unoccupied orbitals.
 3. TDKS 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

(Take xc functional from static DFT and evaluate with time-dependent density)

2 hom
d exc (n )
ALDA:
Vxc (r, t )  Vxc  n r, t   
ALDA LDA

dn 2 n  n ( r ,t )
 3. TDKS Time-dependent selfconsistency (1)

start with
propagate
selfconsistent
until here
KS ground state

t0 T time

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

3. TDKS Numerical time Propagation

t :  j  r, t  t   e  j  r, t 
 iHˆ t
Propagate a time step

iHˆ t 1  iHˆ t 2
Crank-Nicholson algorithm: e 
1  iHˆ t 2

1  i
2
  
tHˆ  j  r, t  t   1  2i tHˆ  j  r, t 

Problem: Ĥ must be evaluated at the mid point t  t 2

But we know the density only for times t
3. TDKS Time-dependent selfconsistency (2)

Predictor Step:

 j t  (j1)  t  t   Hˆ (1)  t  t 

nth Corrector Step:

 j t  ( n 1)
j  t  t   H  t  t 
ˆ ( n 1)

Hˆ  t  t 2  
1
2
 Hˆ  t   Hˆ ( n )  t  t  
Selfconsistency is reached if n t  remains unchanged for t   t0 , T 
upon addition of another corrector step in the time propagation.
3. TDKS Summary of 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:  j
(0)

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:  r , t  n r , t
j  

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

 3. TDKS Example: two electrons on a 2D quantum strip

initial-state density
hard walls
periodic exact
boundaries
LDA
(travelling
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

L
C.A. Ullrich, J. Chem. Phys. 125, 234108 (2006)
 3. TDKS Construction of the exact xc potential

Step 1: solve full 2-electron Schrödinger equation

 12  22 1   
   V  z1 ,t   V  z2 ,t      i    r1 , r2 ,t   0
 2 2 r1  r2 t 

Step 2: calculate the exact time-dependent density

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

s1 ,s2

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 
3. TDKS 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
3. TDKS 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
● Nonadiabatic xc effects can become important (see later)
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

 4. Memory Memory dependence

functional dependence on history, n(r t’<t),

and on initial states

Almost all calculations today ignore this, and use an “adiabatic approximation” :

Just take xc functional from static DFT and evaluate on instantaneous density

vxc

But what about the exact functional?

 4. Memory Example of history dependence

Eg. Time-dependent Hooke’s atom –exactly solvable

2 electrons in parabolic well,

time-varying force constant

k(t) =0.25 – 0.1*cos(0.75 t)

parametrizes
density
Any adiabatic (or even
semi-local-in-time)
approximation would
incorrectly predict the
same vc at both times.

Hessler, Maitra, Burke, (J. Chem. Phys, 2002); Wijewardane & Ullrich, (PRL 2005); Ullrich (JCP, 2006)

• Development of History-Dependent Functionals: Dobson, Bunner & Gross (1997),

Vignale, Ullrich, & Conti (1997), Kurzweil & Baer (2004), Tokatly (2005)
 4. Memory Example of initial-state dependence

A non-interacting example:
Periodically driven HO

Re and Im
parts of 1st and
If we start in different 0’s, can 2nd Floquet
we get the same n(r t) by orbitals
evolving in different potentials?
Yes!
Doubly-occupied
Floquet orbital
with same n
• Say this is the density of an interacting
system. Both top and middle are possible
KS systems.
 vxc different for each. Cannot be captured
by any adiabatic approximation

( Consequence for Floquet DFT: No 1-1 mapping between densities and time-
periodic potentials. )

Maitra & Burke, (PRA 2001)(2001, E); Chem. Phys. Lett. (2002).
 4. Memory Time-dependent optimized effective potential

t
 
N
0  i   dt  d 3 r  Vxc (r, t )  u xcj (r, t )
j 1  

  k (r, t )k* (r, t ) j (r, t ) *j (r, t )  c.c.
k 1

1 Axc i  
where u xcj (r, t )  *
 j (r, t )  j (r, t )

1 N
 *
 r , t    r , t   k  r , t 
*

u xj  r, t    *  
j k
exact exchange: d r
3

 j  r, t  k 1 r  r

C.A.Ullrich, U.J. Gossmann, E.K.U. Gross, PRL 74, 872 (1995)

H.O. Wijewardane and C.A. Ullrich, PRL 100, 056404 (2008)
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

 5. Linear Response 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)
 5. Linear Response Matrix equations (a.k.a. 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

Useful tools for analysis: “single-pole” and “small-matrix” approximations (SPA,SMA)

Zoom in on a single KS excitation, q = i a

Well-separated single excitations: SMA

When shift from bare KS small: SPA

 5. Linear Response How it works: atomic excitation energies

TDDFT linear response from

exact helium KS ground state: LDA + ALDA lowest excitations
Exp. full matrix SMA SPA

Vasiliev, Ogut, Chelikowsky, PRL 82, 1919 (1999)

Look at other
functional approxs
(ALDA, EXX), and
also with SPA. All
From Burke & Gross, (1998); Burke, Petersilka &Gross (2000)
quite similar for He.
5. Linear response General trends

Energies typically to within about “0.4 eV”

Bonds to within about 1%

Dipoles good to about 5%

Vibrational frequencies good to 5%

Cost scales as N3, vs N5 for wavefunction methods of comparable

accuracy (eg CCSD, CASSCF)

Available now in many electronic structure codes

Unprecedented balance between accuracy and efficiency

TDDFT Sales Tag
5. Linear response Examples
Can study big molecules with TDDFT !
Optical Spectrum of DNA fragments
d(GC) -stacked pair

HOMO LUMO

D. Varsano, R. Di Felice, M.A.L. Marques, A Rubio, J. Phys. Chem. B 110, 7129 (2006).
5. Linear response Examples

Circular dichroism spectra of chiral

fullerenes: D2C84

F. Furche and R. Ahlrichs, JACS 124, 3804 (2002).

 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

6. TDDFT in solids Excitations in finite and extended systems

 0 nˆ  r   j  j nˆ  r 0 
  r, r,    lim   c.c.     
 0
 j   E j  E0  i  

j
The full many-body response function has poles at the exact excitation energies

Im  Im 
finite extended

x xx x x
Re  Re 

► Discrete single-particle excitations merge into a continuum

(branch cut in frequency plane)
► New types of collective excitations appear off the real axis
(finite lifetimes)
 6. TDDFT in solids Metals vs. insulators

plasmon

Excitation spectrum of simple metals:

● single particle-hole continuum

(incoherent) Optical excitations
● collective plasmon mode of insulators:

● interband transitions
● excitons (bound
electron-hole pairs)
6. TDDFT in solids Excitations in bulk metals

Plasmon dispersion of Al

Quong and Eguiluz, PRL 70, 3955 (1993)

►RPA (i.e., Hartree) gives already

reasonably good agreement
►ALDA agrees very well with exp.

In general, (optical) excitation processes in (simple) metals are very well

described by TDDFT within ALDA.

Time-dependent Hartree already gives the dominant contribution, and

fxc typically gives some (minor) corrections.

This is also the case for 2DEGs in doped semiconductor heterostructures

6. TDDFT in solids Semiconductor heterostructures

●semiconductor heterostructures are

grown with MBE or MOCVD
●control and design through layer-by-layer
variation of material composition
●widely used class or materials:
III-V compounds

Interband transitions: CB lower edge

of order eV
(visible to near-IR)

Intersubband transitions:
of order meV
(mid- to far-IR)
VB upper edge
6. TDDFT in solids n-doped quantum wells

● Donor atoms separated from quantum well: modulation delta doping

● Total sheet density Ns typically ~1011 cm-2

6. TDDFT in solids Collective excitations

Intersubband charge and spin

plasmons: ↑ and ↓ densities
in and out of phase
6. TDDFT in solids Electronic ground state: subband levels

Effective-mass approximation: m*  m e*  e / 
(for GaAs :   0.067,   13)

Electrons in a quantum well: plane waves in x-y plane, confined along z

 1 iq||r||  2 q||2
 jq|| (r )  e  j ( z) with energies E jq||   j
A 2m *
quantum well
confining potential

 2 d 2 
 2
 Vconf ( z )  VH ( z )  Vxc ( z ) j ( z )   j j ( z )
LDA

 2m * dz 
6. TDDFT in solids Quantum well subbands

k>0
k=0
 6. TDDFT in solids Intersubband plasmon dispersions

charge plasmon
experiment
ω (meV)

spin plasmon

k (Å-1)

C.A.Ullrich and G.Vignale, PRL 87, 037402 (2002)

6. TDDFT in solids Optical absorption of insulators

Silicon

RPA and ALDA both bad!

►absorption edge red shifted

(electron self-interaction)

►first excitonic peak missing

(electron-hole interaction)

Why does the ALDA fail??

G. Onida, L. Reining, A. Rubio, RMP 74, 601 (2002)

S. Botti, A. Schindlmayr, R. Del Sole, L. Reining, Rep. Prog. Phys. 70, 357 (2007)
 6. TDDFT in solids Optical absorption of insulators: failure of ALDA

Optical absorption requires imaginary part of macroscopic dielectric function:

Im  mac    limVG  q  Im  GG 

q 0

VG , G  0
where    KS   KS V  f xc   , VG  
 0, G  0

q  0 limit: ~ q2 Long-range excluded, Needs 1 q

2

so RPA is ineffective component to

correct 
KS

But ALDA is constant

for q  0 :
f xcALDA  lim f xchom  q,   0 
q 0
 6. TDDFT in solids Long-range XC kernels for solids


● LRC (long-range correlation) kernel
(with fitting parameter α):
f xcLRC  q   
q2
2

 f   r   r  
k k
*
k

● TDOEP kernel (X-only): f xOEP  r, r   k

2 r  r  n  r  n r  
Simple real-space form: Petersilka, Gossmann, Gross, PRL 76, 1212 (1996)
TDOEP for extended systems: Kim and Görling, PRL 89, 096402 (2002)

● “Nanoquanta” kernel (L. Reining et al, PRL 88, 066404 (2002)

f BSE
xc  q  0, G, G     vkck; q  0 F
1
G
BSE
vck ,vck      vk ck ; q  0
* 1
G
vck ,vck 

pairs of KS matrix element of screened

wave functions Coulomb interaction (from
Bethe-Salpeter equation)
 6. TDDFT in solids Optical absorption of insulators, again

Kim & Görling

Silicon
Reining et al.

F. Sottile et al., PRB 76, 161103 (2007)

6. TDDFT in solids Extended systems - summary

► TDDFT works well for metallic and quasi-metallic systems already

at the level of the ALDA. Successful applications for plasmon modes
in bulk metals and low-dimensional semiconductor heterostructures.

► TDDFT for insulators is a much more complicated story:

● ALDA works well for EELS (electron energy loss spectra), but
not for optical absorption spectra

● difficulties originate from long-range contribution to fxc

● some long-range XC kernels have become available,

but some of them are complicated. Stay tuned….

● Nonlinear real-time dynamics including excitonic effects:

TDDFT version of Semiconductor Bloch equations
V.Turkowski and C.A.Ullrich, PRB 77, 075204 (2008) (Wednesday P13.7)
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

7. Where the usual approxs. fail Ailments – and some Cures (I)

meaning, semi-local in space

and local in time

Rydberg states Local/semilocal approx inadequate.

Need Im fxc to open gap.
Polarizabilities of long-chain molecules
Can cure with orbital- dependent fnals
Optical response/gap of solids (exact-exchange/sic), or TD current-
DFT

Double excitations Adiabatic approx for fxc fails.

Long-range charge transfer Can use frequency-dependent

kernel derived for some of these
Conical Intersections cases
 7. Where the usual approxs. fail Ailments – and some Cures (II)

Single-determinant constraint of KS
Quantum control phenomena leads to unnatural description of the
true state  weird xc effects

Other strong-field phenomena ? ? Memory-dependence in vxc[n;](r t)

Observables that are not directly related Need to know observable as

to the density, eg NSDI, NACs… functional of n(r t)

Coulomb blockade Lack of derivative discontinuity

Coupled electron-ion dynamics

Lack of electron-nuclear correlation in Ehrenfest,
but surface-hopping has fundamental problems
 7. Where the usual approxs. fail Double Excitations
Excitations of interacting systems generally involve mixtures of (KS) SSD’s
that have either 1,2,3…electrons in excited orbitals.

single-, double-, triple- excitations

Now consider:

 – poles at true states that are mixtures of singles, doubles, and higher excitations

S -- poles only at single KS excitations, since one-body operator can’t

connect Slater determinants differing by more than one orbital.

has more poles than s

? How does fxc generate more poles to get states of multiple excitation character?
 7. Where the usual approxs. fail Double Excitations

Exactly Solve a Simple Model: one KS single (q) mixing with a nearby double (D)

Invert and insert into Dyson-like eqn for kernel dressed SPA (i.e. -dependent):

Strong non-adiabaticity!
 7. Where the usual approxs. fail Double Excitations

General case: Diagonalize many-body H in KS subspace near the double ex of

interest, and require reduction to adiabatic TDDFT in the limit of weak coupling of
the single to the double 

usual adiabatic matrix element

dynamical (non-adiabatic)
correction

NTM, Zhang, Cave,& Burke JCP (2004), Casida JCP (2004)

 7. Where the usual approxs. fail Double Excitations
Example: Short-chain polyenes
Lowest-lying excitations notoriously difficult to calculate due to significant
double-excitation character.
Cave, Zhang, NTM, Burke, CPL (2004)

• Note importance of accurate double-excitation description in coupled electron-ion

dynamics – propensity for curve-crossing
Levine, Ko, Quenneville, Martinez, Mol. Phys. (2006 )
 7. Where the usual approxs. fail Long-Range Charge-Transfer Excitations

Example: Dual Fluorescence in DMABN in Polar Solvents

Rappoport & Furche,

JACS 126, 1277 (2004).

“normal” “anomalous”
“Local” Excitation (LE) Intramolecular Charge Transfer (ICT)

TDDFT resolved the long debate on ICT structure (neither “PICT” nor “TICT”),
and elucidated the mechanism of LE -- ICT reaction

Success in predicting ICT structure – How about CT energies ??

 7. Where the usual approxs. fail Long-Range Charge-Transfer Excitations
TDDFT typically severely underestimates long-range CT energies

ro ce ss in ough
p o r tant p , large en ly
Im
o l e cules ay be on
biom DDFT m
a t T roac h!
th p
a s i b le ap
fe

Eg. Zincbacteriochlorin-Bacteriochlorin
complex
(light-harvesting in plants and purple
bacteria)
Dreuw & Head-Gordon, JACS 126 4007, (2004).

TDDFT predicts CT states energetically well below local fluorescing states.

Predicts CT quenching of the fluorescence.
! Not observed !

TDDFT error ~ 1.4eV

 7. Where the usual approxs. fail Long-Range Charge-Transfer Excitations

Why do the usual approximations in TDDFT fail for these excitations?

We know what the exact energy for charge transfer at long range should be:

exact

Why TDDFT typically severely underestimates this energy can be seen in SPA

-As,2 -I1 ~0 overlap

i.e. get just the bare KS orbital energy difference: missing xc contribution to
acceptor’s electron affinity, Axc,2, and -1/R
(Also, usual g.s. approxs underestimate I)
 7. Where the usual approxs. fail Long-Range Charge-Transfer Excitations

What are the properties of the unknown exact xc kernel that must be well-
modelled to get long-range CT energies correct ?

 Exponential dependence on the fragment separation R,

fxc ~ exp(aR)

 For transfer between open-shell species, need strong frequency-dependence.

step
“LiH”
Step in Vxc re-aligns the 2 atomic
HOMOs  near-degeneracy of
molecular HOMO & LUMO  static
correlation, crucial double excitations 
frequency-dependence!

(It’s a rather ugly kernel…)

Gritsenko & Baerends (PRA, 2004), Maitra (JCP, 2005), Tozer (JCP, 2003)
Tawada et al. (JCP, 2004)
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

8. TDCDFT The adiabatic approximation, again

● In general, the adiabatic approximation works well for excitations

which have an analogue in the KS system (single excitations)

● formally justified only for infinitely slow electron dynamics. But

why is it that the frequency dependence seems less important?

The frequency scale of fxc is set by correlated multiple

excitations, which are absent in the KS spectrum.

● Adiabatic approximation fails for more complicated excitations

(multiple, charge-transfer)

● misses dissipation of long-wavelength plasmon excitations

Fundamental question: what is the proper

extension of the LDA into the dynamical regime?
8. TDCDFT Nonlocality in space and time

Visualize electron dynamics as the motion (and deformation)

of infinitesimal fluid elements:


 r ', t'
r,t

Nonlocality in time (memory) implies nonlocality in space!

Dobson, Bünner, and Gross, PRL 79, 1905 (1997)

I.V. Tokatly, PRB 71, 165105 (2005)
 8. TDCDFT Ultranonlocality in TDDFT

 
 d r n r , t Vxc  r , t   0
3 
Zero-force theorem:

    
 d r ' n0  r ' f xc  r , r ' ,    Vxc,0  r 
3
Linearized form:

If the xc kernel has a finite range, we can write for slowly varying systems:
  3   
n0  r   d r ' f xc  r , r ' ,    Vxc,0  r 

 f hom
xc  
k  0,  
l.h.s. is frequency-dependent, r.h.s is not: contradiction!

f xc  r , r ' ,   has infinitely long spatial range!
8. TDCDFT Ultranonlocality and the density

n x0 , t 
●

x0 x

An xc functional that depends only on the local density

(or its gradients) cannot see the motion of the entire slab.

A density functional needs to have a long range to see

the motion through the changes at the edges.
8. TDCDFT Harmonic Potential Theorem – Kohn’s mode

J.F. Dobson, PRL 73, 2244 (1994)

A parabolically confined, interacting N-electron system can carry

out an undistorted, undamped, collective “sloshing” mode,
 where

 

n r , t   n0 r  R t  , with the CM position R  t .
8. TDCDFT Point of view of local density

global local com-

translation pression and
rarefaction

Vxc “rides along”: Vxc is retarded:

undamped motion damped motion

xc functionals based on local density can’t distinguish the two cases!

8. TDCDFT Point of view of local current

uniform velocity oscillating velocity

much better chance to capture the physics correctly!

8. TDCDFT Upgrading TDDFT: time-dependent Current-DFT


Vxc  r , t 

n r , t 
nonlocal

nonlocal nonlocal
  n 
 j    Axc
t Vxc 
t
  
jr,t local
Axc  r , t 


n  r ' , t 

       
j  r , t   jL  r , t   jT  r , t  , jL  r , t    r  r'
4
● Continuity equation only gives the longitudinal current
● TDCDFT gives also the transverse current
● We can find a short-range current-dependent xc vector potential
8. TDCDFT Basics of TDCDFT

generalization of RG theorem: Ghosh and Dhara, PRA 38, 1149 (1988)

G. Vignale, PRB 70, 201102 (2004)

ˆ 
1  1   2

H int  t     pi  c Aext  ri , t   Vext  ri , t     U  ri  rj 
   
i 2  i j

full current can be     

represented by j  r , t   jL  r , t   jT  r , t 
a KS system

 1 

  2

 
H KS  t     pi  c AKS  ri , t   VKS  ri , t  
ˆ 1

i 2 
uniquely determined up to gauge transformation
 8. TDCDFT TDCDFT in the linear response regime

 
         
j1  r ,     d r '  KS  r , r ' ,   Aext,1  r ,    AH ,1  r ,    Axc,1  r ,  
3

KS current-current response tensor: diamagnetic + paramagnetic part

1  fk  f j
   r , r ' ,    n0  r   r  r '    P  r  P  r '
    kj  jk 

2 j , k  k   j    i

   
where Pkj   k*  r    j  r    j  r    k*  r 
8. TDCDFT Effective vector potential

 
Aext ,1  r ,   : external perturbation. Can be a
true vector potential, or a gauge  1 
transformed scalar perturbation: Aext ,1  Vext ,1
i
  
 3  ' j  r ' ,  
 
AH ,1  r ,    2 
d r'   gauge transformed
 i  r  r' Hartree potential

   
Axc ,1  r ,     d r ' f xc  r , r ' ,   j  r ' ,  
3  the xc kernel is
now a tensor!

 ALDA   ALDA  
 
ALDA: Axc ,1  r ,    2 
d r ' f xc  r , r ' ' j  r ' ,  
3

 i 
8. TDCDFT TDCDFT beyond the ALDA: the VK functional

G. Vignale and W. Kohn, PRL 77, 2037 (1996)

G. Vignale, C.A. Ullrich, and S. Conti, PRL 79, 4878 (1997)

   ALDA  c   
Axc ,1  r ,    Axc ,1  r ,        xc  r ,  
in0  r 
xc viscoelastic stress tensor:

~  2   ~  
 xc, jk   xc   j v1,k   k v1, j    v1 jk    xc  v1 jk
 3 

v  r ,    j  r ,   / n0  r  velocity field
 

● automatically satisfies zero-force theorem/Newton’s 3rd law

● automatically satisfies the Harmonic Potential theorem
● is local in the current, but nonlocal in the density
● introduces dissipation/retardation effects
8. TDCDFT XC viscosity coefficients

2
n
~xc  n,     f xcT  n,  
i
~ n2  L 4 T d 2 excunif 
 xc  n,      f xc  n,    f xc  n,    
i  3 dn 2 

In contrast with the classical case, the xc viscosities have both real
and imaginary parts, describing dissipative and elastic behavior:

S xc    shear modulus
       
~ reflect the
stiffness of
i Fermi surface

Bxcdyn    dynamical
against defor-
~
        bulk modulus mations

i
8. TDCDFT xc kernels of the homogeneous electron gas

Im f xcL Re f xcL

Im f xcT Re f xcT

GK: E.K.U. Gross and W. Kohn, PRL 55, 2850 (1985)

NCT: R. Nifosi, S. Conti, and M.P. Tosi, PRB 58, 12758 (1998)
QV: X. Qian and G. Vignale, PRB 65, 235121 (2002)
8. TDCDFT Static limits of the xc kernels

2 unif
d exc (n) 4 S xc (0)
f xc (0) 
L
2

dn 3 n2
S xc (0)
f xc (0) 
T

n2

The shear modulus of the electron liquid does not disappear for   0.
(as long as the limit q0 is taken first). Physical reason:
● Even very small frequencies <<EF are large compared
to relaxation rates from electron-electron collisions.
● The zero-frequency limit is taken such that local
equilibrium is not reached.
● The Fermi surface remains stiff against deformations.
 8. TDCDFT TDCDFT for conjugated polymers

ALDA overestimates
polarizabilities of long
molecular chains.
The long-range VK
functional produces
a counteracting field,
due to the finite shear
modulus at   0.

M. van Faassen et al., PRL 88, 186401 (2002) and JCP 118, 1044 (2003)
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

9. Transport DFT and nanoscale transport

Koentopp, Chang, Burke, and Car (2008)


2
I   dE T  E   f L  E   f R  E   two-terminal Landauer formula
 
Transmission coefficient, usually obtained from
DFT-nonequilibrium Green’s function

Problems: ● standard xc functionals (LDA,GGA) inaccurate

● unoccupied levels not well reproduced in DFT
transmission peaks can come out wrong
conductances often much overestimated
need need better functionals (SIC, orbital-dep.)
and/or TDDFT
 9. Transport TDDFT and nanoscale transport: weak bias

    
Current response: j  r ,    d r'  0  r , r ' ,  Eeff  r ' , 
3

T0   F  3
d r' Eext     EH  r ' ,   E xc  r ' ,  
 
I    0  

XC piece of voltage drop: Current-TDDFT
R dyn 4
 2 
  z n
dz
2

4
Sai, Zwolak, Vignale, Di Ventra, 3e Ac n
PRL 94, 186810 (2005)
dynamical resistance: ~10% correction
 9. Transport TDDFT and nanoscale transport: finite bias

(A) Current-TDDFT and Master equation (B) TDDFT and Non-equilibrium

Green’s functions
Burke, Car & Gebauer, PRL 94, 146803 (2005)
Stefanucci & Almbladh, PRB 69, 195318 (2004)

● periodic boundary conditions ● localized system

(ring geometry), electric field ● density as basic variable
induced by vector potential A(t) ● steady current via electronis
● current as basic variable dephasing with continuum of
● requires coupling to phonon the leads
bath for steady current

► (A) and (B) agree for weak bias and small dissipation
► some preliminary results are available – stay tuned!
 Outline

1. A survey of time-dependent phenomena C.U.

2. Fundamental theorems in TDDFT N.M.

3. Time-dependent Kohn-Sham equation C.U.

4. Memory dependence N.M.

5. Linear response and excitation energies N.M.

6. Optical processes in Materials C.U.

7. Multiple and charge-transfer excitations N.M.

8. Current-TDDFT C.U.

9. Nanoscale transport C.U.

10. Strong-field processes and control N.M.

10. Strong-field processes TDDFT for strong fields

In addition to an approximation for vxc[n;0,0](r,t), also need an

approximation for the observables of interest.

 Is the relevant KS quantity physical ?

Certainly measurements involving only density (eg dipole moment) can

be extracted directly from KS – no functional approximation needed for
the observable. But generally not the case.

We’ll take a look at:

High-harmonic generation (HHG)
Above-threshold ionization (ATI)
Non-sequential double ionization (NSDI)
Attosecond Quantum Control
Correlated electron-ion dynamics
10. Strong-field processes High Harmonic Generation

HHG: get peaks at

odd multiples of
laser frequency

Eg. He

TDHF correlation reduces

peak heights by ~ 2 or 3
L’Huillier (2002)

Measures dipole moment,

|d()|2 = ∫ n(r,t) r d3r
so directly available from TD KS
system

Erhard & Gross, (1996)

 10. Strong-field processes Above-threshold ionization

ATI: Measure
kinetic energy of
ejected electrons

Eg. Na-clusters

L’Huillier (2002)

= 1064 nm
I=6 • TDDFT is the only computationally
x 10 W/cm2
12
feasible method that could compute ATI for
pulse length something as big as this!
30 Up 25 fs
• ATI measures kinetic energy of electrons
– not directly accessible from KS. Here,
approximate T by KS kinetic energy.
•TDDFT yields plateaus much longer than
the 10 Up predicted by quasi-classical one-
Nguyen, Bandrauk, and Ullrich, PRA electron models
69, 063415 (2004).
 10. Strong-field processes Non-sequential double ionization

Exact c.f. TDHF 1

TDDFT
1
2 2

TDDFT c.f. TDHF

Lappas & van Leeuwen (1998),

Lein & Kummel (2005)

Knee forms due to a switchover from a sequential to a non-sequential

(correlated) process of double ionization.
Knee missed by all single-orbital theories eg TDHF

TDDFT can get it, but it’s difficult :

• Knee requires a derivative discontinuity, lacking in most approxs
• Need to express pair-density as purely a density functional – uncorrelated
expression gives wrong knee-height. (Wilken & Bauer (2006))
 10. Strong-field processes Electronic quantum control
,
Is difficult: Consider pumping He from (1s2)  (1s2p)

Problem!! The KS state remains doubly-occupied throughout – cannot evolve into a

singly-excited KS state.

Simple model: evolve two electrons in a harmonic potential from ground-state

(KS doubly-occupied 0) to the first excited state (0,1) :

TDKS

KS system achieves the target excited-state density, but with a doubly-occupied

ground-state orbital !! The exact vxc(t) is unnatural and difficult to approximate.

Maitra, Woodward, & Burke (2002), Werschnik & Gross (2005), Werschnik, Gross & Burke (2007)
 10. Strong-field processes Coupled electron-ion dynamics
Classical nuclei coupled to quantum electrons, via Ehrenfest coupling, i.e.

=
Eg. Collisions of O atoms/ions with
graphite clusters
Freely-available TDDFT code for
strong and weak fields:

http://www.tddft.org
Castro, Appel, Rubio,
Lorenzen, Marques,
Oliveira, Rozzi,
Andrade, Yabana,
Bertsch

Isborn, Li. Tully, JCP 126, 134307 (2007)

 10. Strong-field processes Coupled electron-ion dynamics

Classical Ehrenfest method misses electron-nuclear correlation

, re la xation,
y
(“branching” of trajectories) p h o t o c hemistr os,
! e ss e n tial for
b r a n c h ing rati
! ansfer,
t r on tr ces...
elec r s u rf a
s nea
reaction

How about Surface-Hopping a la Tully with TDDFT ?

Simplest: nuclei move on KS PES between hops. But, KS PES ≠ true PES,
and generally, may give wrong forces on the nuclei.

Should use TDDFT-corrected PES (eg calculate in linear response).

But then, trajectory hopping probabilities cannot be simply extracted –

e.g. they depend on the coefficients of the true  (not accessible in TDDFT),
and on non-adiabatic couplings.

Craig, Duncan, & Prezhdo PRL 2005, Tapavicza, Tavernelli, Rothlisberger, PRL 2007, Maitra,
JCP 2006
 To learn more…

Time-dependent density functional theory, edited by

M.A.L. Marques, C.A. Ullrich, F. Nogueira, A. Rubio,
K. Burke, and E.K.U. Gross, Springer Lecture Notes
in Physics, Vol. 706 (2006)

(see handouts for TDDFT literature list)

Upcoming TDDFT conferences:

● 3rd International Workshop and School on TDDFT   

Benasque, Spain, August 31 - September 15, 2008
http://benasque.ecm.ub.es/2008tddft/2008tddft.htm

● Gordon Conference on TDDFT, Summer 2009

http://www.grc.org
 Acknowledgments

Collaborators: Students/Postdocs:

• Giovanni Vignale (Missouri) • Harshani Wijewardane

• Kieron Burke (Irvine) • Volodymyr Turkowski
• Ilya Tokatly (San Sebastian) • Ednilsom Orestes
• Irene D’Amico (York/UK) • Yonghui Li
• Klaus Capelle (Sao Carlos/Brazil)
• Meta van Faassen (Groningen) • David Tempel
• Adam Wasserman (Harvard) • Arun Rajam
• Hardy Gross (FU-Berlin) • Christian Gaun
• August Krueger
• Gabriella Mullady
• Allen Kamal