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Department of Physics and Astronomy, University of Missouri, Columbia, MO 65211, USA

(Dated: January 29, 2014)

Time-dependent density-functional theory (TDDFT) is a formally exact approach to the time-

dependent electronic many-body problem which is widely used for calculating excitation energies.

We present a survey of the fundamental framework, practical aspects, and applications of TDDFT.

This paper is mainly intended for non-experts (students or researchers in other areas) who would

like to learn about the present state of TDDFT without going too deeply into formal details.

arXiv:1305.1388v2 [cond-mat.mtrl-sci] 27 Jan 2014

of time-dependent density-functional theory (TDDFT).

The purpose of the paper is to explain in a nutshell what We consider a system of N interacting electrons that

TDDFT is and what it can do. We will discuss the basics is described by the nonrelativistic Schrödinger equation:

of the formal framework of TDDFT as well as the cur-

rent state of the art, skipping over details of the proofs, Ĥ0 Ψj (r1 , . . . , rN ) = Ej Ψj (r1 , . . . , rN ) ,

j = 0, 1, 2, . . . .

and highlight some of the most important applications. (1)

Readers who would like a more detailed treatment and For a given D-dimensional system, the jth eigenstate

more literature references are encouraged to consult re- Ψj (r1 , . . . , rN ) is a function of DN spatial variables. In

cent books [1, 2] and review articles [3–5]. the following, we use the abbreviation Ψj . Of particular

TDDFT is a theoretical approach to the dynamical interest to us is the ground-state wave function Ψgs .

quantum many-body problem; it can be used to describe The many-body Hamiltonian is given by

quantum systems that are not stationary. As a conse-

Ĥ = T̂ + V̂ + Ŵ , (2)

quence, TDDFT provides formally exact and practically

convenient methods to calculate electronic excitation en- where the kinetic-energy and scalar potential operators

ergies. By contrast, density-functional theory (DFT) is a are

ground-state theory: in other words, it is used to find the

ground state of a quantum system and calculate related N N

X ∇2j X

quantities of interest, such as the ground-state energy. T̂ = − , V̂ = v(rj ) , (3)

2

In many, if not most, situations of practical interest, we j=1 j=1

have to determine the ground state of the system before

we can study its dynamics or calculate its excitations. and the electron-electron interaction operator is

The beginnings of ground-state DFT date back to the N

X

years 1964/65 when the famous papers by Hohenberg and Ŵ = w(|ri − rj |) . (4)

Kohn [6] and Kohn and Sham [7] were published. Since i,j=1

i6=j

then, DFT has developed into a dominating method for

electronic structure calculations in physics, chemistry, Notice that we use atomic (Hartree) units throughout,

materials science, and many other areas (see Ref. [8] for i.e., m = e = h̄ = 1. The electron-electron interaction is

a recent up-to-date account of DFT). Although TDDFT usually taken to be the Coulomb interaction, w(|r−r′ |) =

is of much more recent origin [9], it now has reached a 1/|r − r′ |, but other forms of two-particle interactions, or

similar status for calculating electronic excitations. zero interactions, are also possible.

TDDFT uses many familiar concepts from DFT, most The single-particle potential v(r) describes the total

prominently, the Kohn-Sham idea of replacing the real potential acting on the electrons. If one is interested in

interacting many-body system by a noninteracting sys- describing the properties of matter (atoms, molecules,

tem that reproduces the same density. But there are also or solids), v(r) is the sum of the Coulomb potentials of

many concepts that are unique to the time-dependent the atomic nuclei. However, to define the formal frame-

case, such as memory and initial-state dependence. To work of DFT it is not necessary to specify where the

gain a thorough understanding of TDDFT it is hence potential comes from, as long as it has a mathematically

advisable to begin with a study of the basic concepts of well-behaved form.

DFT. We refer the reader to the very nice introductions From the solutions of the Schrödinger equation we cal-

to DFT by Capelle [10] and by Burke and Wagner [11]. culate the expectation value of an observable in the jth

There exist a number of books on DFT, some of which are eigenstate:

very accessible to newcomers in the field [12, 13], others

are more advanced [14]. Oj = hΨj |Ô|Ψj i. (5)

2

tum mechanical observable.

Let us make two remarks on our formulation of the v(x)

many-body problem.

(a) We implicitly made the Born-Oppenheimer approx-

imation (see Section VII C). In other words, if our system

contains nuclear degrees of freedom (as is the case in all

forms of real matter), we treat them classically. The

x

many-body wave functions therefore depend only on the

electronic coordinates (r1 , . . . , rN ), and the nuclei only 0.5 0 0.5

act as sources of scalar potentials. In Section VIII we

FIG. 1. The density n0 (x) = cos2 (πx) + cos2 (3πx) (dashed

will briefly discuss what happens if this approximation

line, scaled by a factor 60), for − 21 < x < 12 , is the ground-

is not made and the electronic and nuclear degrees of state density of the potential v(x) (full line) which was con-

freedom are coupled. structed using Eq. (8).

(b) We have not indicated any spin indices, which was

done mainly for notational simplicity. In other words,

Ψj (r1 , . . . , rN ) describes spinless electrons. Including ity density as n0 (r) = |ϕ0 (r)|2 . But now imagine the

spin, the many-body wave function can be written as reverse situation: we are given a density function n0 (r),

Ψ(x1 , . . . , xN ), where xi = (ri , σi ) denotes the spatial normalized to 1, and we ask in what potential this is the

and spin coordinate of the ith electron. ground-state density.p Assuming that the wave functions

are real so ϕ0 (r) = n0 (r), the Schrödinger equation (7)

is easily inverted, and we obtain

B. The basic idea behind DFT

∇2 n0 (r) |∇n0 (r)|2

Everything we wish to know about our system (en- v(r) = − . (8)

4n0 (r) 8n0 (r)2

ergy, geometry, excitation spectrum, etc.) can be ob-

tained from the wave functions, see Eq. (5). The exact A one-dimensional example is given in Fig. 1.

wave functions can be calculated if the system is small, What has been accomplished? From the ground-state

with no more than one or two electrons, but this becomes density n0 (r) we were able to reconstruct the potential

very difficult if N is greater than that: the many-body v(r). But this means that we have reconstructed the

Schrödinger equation becomes too hard to solve, and the Hamiltonian Ĥ of the system, and we can thus solve the

usefulness of the wave function itself becomes more and Schrödinger equation (7) and get all the wave functions!

more questionable for large N [15]. This logical chain can be represented as follows:

There exist many approaches to find approximate so-

lutions of the many-body problem. So-called “wave- n0 (r) → v(r) → Ĥ → {Ψj }. (9)

function based techniques” such as Hartree-Fock (HF) or

configuration-interaction (CI) attempt to find variational The reconstruction of the potential from the density is

solutions of the Schrödinger equation using expansions of easy for one-electron systems. For interacting systems

the wave function in terms of Slater determinants. This with many electrons there is no explicit formula such as

approach has been very successful in theoretical chem- Eq. (8). Nevertheless, there exists a unique potential for

istry, but has its limitations for large systems. each mathematically well-behaved density function such

The essence of the density-functional approach is that that it is the ground-state density in this potential. This

it is in principle possible to obtain all desired information was proved by Hohenberg and Kohn in 1964 [6].

about an N -electron system without having to calculate The Hohenberg-Kohn theorem states that it is impossi-

its full wave function: instead, all one needs is the one- ble for two different potentials, v(r) and v ′ (r), to produce

particle probability density of the ground state, the same ground-state density (v ′ is considered to be dif-

Z Z ferent from v if it is not just v shifted by a constant).

n0 (r) = N d3 r2 . . . d3 rN |Ψgs (r, r2 , . . . , rN )|2 . (6) In other words, the relationship between potentials and

ground-state densities is one-to-one:

This can be mathematically proven (see below), but

n0 (r) ↔ v(r) . (10)

before doing so it is helpful to give a simple illustra-

tion. Consider a one-electron system which satisfies the The proof of this theorem is relatively straightforward,

Schrödinger equation making use of the Rayleigh-Ritz minimum principle. It

∇2

can be found in any textbook on DFT, so we won’t repeat

− + v(r) ϕj (r) = εj ϕj (r) . (7) it here.

2

Formally, this logical dependence of the wave functions

The usual procedure is to solve this equation for a given on the ground-state density constitutes a functional rela-

potential v(r) and determine the ground-state probabil- tionship, which is written as Ψj [n0 ]. Hence, the name

3

density-functional theory. Every quantum mechanical And whatever is left is called the exchange-correlation

observable thus can be written as a density functional. (xc) potential, vxc [n](r), so that

In particular, the total energy functional of a system

with potential v0 (r) is vs [n](r) = v0 (r) + vH (r) + vxc [n](r) . (16)

Ev0 [n] = hΨ[n]|T̂ + V̂0 + Ŵ |Ψ[n]i , (11) It turns out that the solution of the Kohn-Sham equation

(14)—that is, the density (13)— is precisely that density

where n is some N -electron density and Ψ[n] is that

ground-state wave function which reproduces this den- which minimizes the total energy functional (11). The

connection is made by rewriting the energy as follows:

sity. The energy functional (10) is minimized by the

ground-state density n0 which belongs to v0 , and then

Z

becomes equal to the ground-state energy: Ev0 [n] = T [n] + d3 r v0 (r)n(r) + W [n]

Ev0 [n] > E0 for n(r) 6= n0 (r) ,

Z

= Ts [n] + d3 rv0 (r)n(r) + (T [n] − Ts [n] + W [n])

Ev0 [n] = E0 for n(r) = n0 (r) . (12) Z

≡ Ts [n] + d3 rv0 (r)n(r) + EH [n] + Exc [n] . (17)

C. The Kohn-Sham approach

Here, T [n] is the kinetic-energy functional of an inter-

The fact that all observables are functionals of the den- acting system, whereas Ts [n] is the kinetic-energy func-

sity opens up the way for an enormous computational tional of a noninteracting system. Neither T [n] nor Ts [n]

simplification, since the density is a function of only D are known as explicit density functionals, but it is very

variables (and not of DN variables as the wave function). straightforward to write down Ts [n] as an explicit func-

But how can we take advantage of this in practice? To tional of the orbitals:

obtain the density one still needs to solve the full many- N

body problem. This means that nothing has been gained, 1X ∗

Ts [n] = − ϕ (r)∇2 ϕj (r) , (18)

unless we find a way to bypass the full Schrödinger equa- 2 j=1 j

tion and obtain the density in some other, easier way, at

least approximately. Fortunately, a very elegant method where the orbitals ϕj (r) come from the Kohn-Sham equa-

exists to do this, known as the Kohn-Sham formalism [7]. tion (14) are are hence implicit density functionals.

We use the following trick: we define a noninteracting In the last line of Eq. (17) we define the Hartree energy

system in such a way that it reproduces the exact ground-

state density of the interacting system. This means that 1 n(r)n(r′ )

Z Z

we can calculate the exact density as the sum of squares EH [n] = d r d3 r′

3

(19)

2 |r − r′ |

of single-particle orbitals,

N and the xc energy as

X

n0 (r) = |ϕj (r)|2 , (13)

Exc [n] = T [n] − Ts [n] + W [n] − EH [n] . (20)

j=1

where the orbitals satisfy the following equation; This shows that the xc potential is given by the following

functional derivative:

∇2

− + vs [n](r) ϕj (r) = εj ϕj (r) . (14)

2 δExc [n]

vxc (r) = . (21)

This equation is known as Kohn-Sham equation; it is for- δn(r)

mally a single-particle Schrödinger equation, like Eq. (7).

It is straightforward to show that the total energy (17)

However, the potential vs is very special: it is defined to

can be expressed as follows:

be that single-particle potential that produces orbitals

which give the exact ground-state density of the inter- N

X Z

acting system via Eq. (13). It is therefore a functional Ev0 [n] = εj − EH [n] − d3 r vxc (r)n(r) + Exc [n] .

of the density, vs [n](r). j=1

The trick is now to write the unknown effective poten- (22)

tial vs [n] in a smart way. No doubt, the given external po-

tential v0 (r) will make a contribution to it. The remain-

der, vs [n] − v0 (r), then accounts for the electronic many- D. Discussion and exact properties

body effects. A large portion of the latter is made by

the classical Coulomb potential associated with a given

Let us now summarize some of the most important

density distribution, also known as the Hartree potential,

properties of the Kohn-Sham approach. Our discussion

n(r′ )

Z

is by no means complete, but the following properties will

vH (r) = d3 r′ . (15)

|r − r′ | be relevant for the time-dependent case as well.

4

is noninteracting, so its total N -particle wave function Nσ

can be written as a single Slater determinant: X

nσ (r) = |ϕjσ (r)|2 . (29)

1 j=1

ΨKS

gs (r1 , . . . , rN ) = √ det{ϕj } . (23)

N! Exact exchange. The xc energy can be decomposed

The Kohn-Sham Slater determinant has only one pur- into exchange and correlation energy. The exact ex-

pose: to reproduce the exact ground-state density when change energy is given by

substituted in Eq. (6). It is not meant to reproduce Nσ Z

1 X X

Z

the exact ground-state wave function, i.e., ΨKS

gs 6= Ψgs in Exexact [n] = − d3 r d3 r′

general. 2 i,j=1

σ=↑,↓

Meaning of the Kohn-Sham energies. The energy

ϕ∗iσ (r)ϕjσ (r′ )ϕiσ (r′ )ϕ∗jσ (r)

eigenvalues εj do not have a rigorous physical meaning, × , (30)

except for the highest occupied eigenvalue. We have |r − r′ |

εN (N ) = E(N ) − E(N − 1) = −I(N ) , (24) where the ϕjσ (r) are the exact Kohn-Sham orbitals.

Exexact is a so-called implicit density functional.

i.e., the highest occupied eigenvalue of the N -particle sys-

tem equals minus the ionization energy of the N -particle

system, and E. DFT in practice

εN +1 (N + 1) = E(N + 1) − E(N ) = −A(N ) , (25) The number of applications of DFT in various ar-

eas of science and engineering is almost impossible to

i.e., the highest occupied eigenvalue of the N + 1-particle count. Nice practical introductions from the perspectives

system equals minus the electron affinity of the N - of chemistry and of materials science, respectively, can

particle system. be found in recent books and review articles [12, 13, 16].

Eigenvalue differences εa − εi , where a labels an unoc- Here, we will only make some general remarks and dis-

cupied single-particle state and i an occupied one, should cuss a couple of representative examples.

not be interpreted as excitation energies of the many- Even though DFT is in principle exact (as we have em-

body system (although they often are). phasized), any practical application necessarily involves

Asymptotic behavior of the Kohn-Sham potential. A two kinds of approximations: (i) the xc energy functional

neutral atom with N electrons has the nuclear poten- Exc [n], and the xc potential following from it via Eq.

tial v0 (r) = −N/r, and its Hartree potential behaves as (21), are not exactly known and need to be approxi-

vH (r) → N/r for r → ∞. If an electron is far away in mated; (ii) the Kohn-Sham equation (14) needs to be

the outer regions of the atom, it should see the Coulomb solved using some computational scheme, which can in-

potential of the remaining positive ion. This implies that troduce various types of numerical inaccuracies.

the xc potential must behave asymptotically as Over the years, many approximate xc functionals

1 have been proposed; some of them using physical ar-

vxc (r) → − (26) guments, constraints and exact conditions, others us-

r

ing parametrizations combined with fitting to reference

for large r, for any finite system. The asymptotic behav- data. Which functional should one choose? This ques-

ior of vxc (r) reflects the fact that the Kohn-Sham formal- tion cannot be easily answered in general [17] but requires

ism is free of self-interaction: for a 1-electron system, the some experience. Practitioners of DFT who use popular

Hartree and xc potential cancel exactly. software packages of quantum chemistry or solid-state

Spin-dependent formalism. In practice, the Kohn- physics often encounter daunting choices between many

Sham formalism is usually written down and applied in different menu options for vxc . Some functionals have

its spin-polarized form, even if the system does not have turned out to be more popular and successful than others,

a net spin polarization. We then have and are typically chosen in the majority of applications.

The xc energy of any system can be written as

∇2

− + v0σ (r) + vH (r) + vxcσ (r) ϕjσ (r) = εjσ ϕjσ (r) , Z

2 Exc [n] = d3 r exc [n](r) , (31)

(27)

where σ =↑, ↓. Here, the external potential v0σ carries

a spin index, which could come from a static magnetic where exc [n](r) is the xc energy density, whose depen-

field, and the spin-polarized xc potential is defined as a dence on the density is, in general, nonlocal: exc at a

functional of the spin-up and spin-down density: particular point r is determined by the density n(r′ ) at

all points in space. The goal is to approximate exc [n](r).

δExc [n↑ , n↓ ] Much of the success of DFT can be attributed to the

vxcσ [n↑ , n↓ ](r) = , (28)

δnσ (r) fact that a very simple approximation, the local-density

5

TABLE I. Mean absolute errors in several molecular proper-

circumstances. The LDA has the following form:

ties calculated for various test sets [22].

Z

LDA

Exc [n] = d3 r ehxc (n(r)) . (32) Formation Ionization Equilibrium Vibrational

enthalpya potentialb bond lengthc frequencyd

Here, the xc energy density of a homogeneous electron

liquid, ehxc (n̄) (which is simply a function of the uniform HF 211.54 1.028 0.0249 136.2

density n̄), is evaluated at the local density at point r of LSDA 121.85 0.232 0.0131 48.9

the actual inhomogeneous physical system: ehxc (n(r)) =

h

LDA BLYP 9.49 0.286 0.0223 55.2

exc (n̄) n̄=n(r) . The so defined Exc

[n] is exact in the

limit where the system becomes uniform, and should be PBE 22.22 0.235 0.0159 42.0

accurate when the system varies only slowly in space. B3LYP 4.93 0.184 0.0104 33.5

The LDA requires ehxc (n̄) as input [18]. We can write

a

ehxc (n̄) = ehx (n̄) + ehc (n̄) , (33) For a test set of 223 molecules (in kcal/mol).

b

For a test set of 223 molecules (in eV), evaluated from the

where the exchange energy density can be calculated ex- total-energy differences between the cation and the

actly using Hartree-Fock theory; the result (for the spin- corresponding neutral, for their respective geometries.

c

unpolarized electron liquid) is For a test set of 96 diatomic molecules (in Å).

d

For a test set of 82 diatomic molecules (in cm−1 ).

1/3

3 3

ehx (n̄) = − n̄4/3 . (34)

4 π The LDA can be improved by including a dependence

not only on the local density itself, but also on gradi-

This gives the following expression for the LDA exchange

ents of the density. This defines the so-called generalized

potential:

gradient approximation (GGA), which has the following

generic form:

" 1/3 Z #

δ 3 3

vxLDA (r) = − d3 r′ n(r′ )4/3

δn(r) 4 π GGA

Z

1/3 Exc [n↑ , n↓ ] = d3 r exc (n↑ (r), n↓ (r), ∇n↑ (r), ∇n↓ (r)) .

3

=− n(r)1/3 . (35) (36)

π There exist hundreds of different GGA functionals, and it

The correlation energy density ehc (n̄) is not exactly is impossible to list all of them here. Among the most fa-

known, but very accurate numerical results exist from mous ones are the B88 exchange functional [23], the LYP

quantum Monte Carlo calculations. Based on these re- correlation functional [24] (which, combined together,

sults, parametrizations for the correlation energy of the give the BLYP functional), and the PBE functional [25].

homogeneous electron liquid have been derived [19–21]. The exchange part of the latter has the following form:

The LDA generally performs very well across the Z

κ

PBE 3 h

board. It produces atomic and molecular total ground- Ex = d rex (n) 1 + κ − , (37)

state energies within 1-5% of the exact value, and yields 1 + βπ 2 s2 /3κ

molecular equilibrium distances and geometries within where s(r) = |∇n(r)|/2n(r)kF (r), kF (r) is the local

about 3%. For solids, Fermi surfaces in metals come out Fermi wavevector, and κ and β are given parameters.

within a few percent, lattice constants of solids within The GGAs have been crucial in the great success story

about 2%, and vibrational frequencies and phonon ener- of DFT over the past couple of decades, due to their accu-

gies are obtained within a few percent as well. racy combined with computational simplicity. However,

On the other hand, the LDA has several shortcom- improvements are still desirable. One of the most im-

ings. For instance, the LDA is not self-interaction free; portant breakthroughs has been the development of the

as a consequence, the xc potential goes to zero exponen- so-called hybrid functionals, which mix in a fraction of

tially fast and not as −1/r [Eq. (26)]. This causes the exact exchange:

Kohn-Sham energy eigenvalues to be too low in magni-

tude in general; in particular, the highest occupied eigen- hybrid

Exc = aExexact + (1 − a)ExGGA + EcGGA , (38)

value εN underestimates the ionization energy typically

by 30–50%. The LDA does not produce any stable neg- where a is a mixing coefficient that has a value of around

ative ions, and it underestimates the band gap in solids. 0.25. The most famous hybrid functional is B3LYP [26],

Dissociation of heteronuclear molecules in LDA produces which nowadays has become the workhorse of compu-

ions with fractional charges. tational chemistry. It should be noted that the exact

Overall, the LDA often gives good results in solid-state exchange mixed in here prevents the easy construction of

physics and materials science, but it is usually not accu- a local xc potential, so hybrid functionals are defined in

rate enough for many chemical applications. the so-called generalized-Kohn-Sham scheme [27, 28].

6

TABLE II. Equilibrium lattice constants of some representa-

strength of range-separated hybrids is that they have the

tive bulk solids [30]. The experimental data includes a sub-

traction of zero-point motion effects. PBEsol is a variant of correct (Hartree-Fock) long-range asymptotic behavior,

the PBE functional [31], and TPSS is a so-called meta-GGA and at the same time take advantage of the good short-

functional, which contains a dependence on density gradients range behavior of LDA or GGA. This, in turn, leads to

and on the kinetic-energy density [32]. a significant improvement in properties such as the po-

larizabilities of long-chain molecules, bond dissociation,

LDA PBE PBEsol TPSS Experiment and, particularly importantly for TDDFT, Rydberg and

charge-transfer excitations (see Section VI C).

Li 3.363 3.429 3.428 3.445 3.449 This concludes our very brief survey of ground-state

Na 4.054 4.203 4.167 4.240 4.210 DFT. Let us now come to the dynamical case.

Cu 3.517 3.628 3.562 3.575 3.595

Si 5.403 5.466 5.431 5.451 5.416 III. SURVEY OF DYNAMICAL PHENOMENA

NaCl 5.465 5.700 5.602 5.703 5.565

The stationary many-body problem was defined in Sec-

MgO 4.168 4.255 4.223 4.237 4.184

tion II A. Solving the Schrödinger equation (1) allows us

to obtain the eigenstates of an N -particle system. The

time-dependent Schrödinger equation is given by

Table I gives an assessment of various approximate xc ∂

functionals, carried out for large molecular test sets [22]. i Ψj (r1 , . . . , rN , t) = Ĥ(t)Ψj (r1 , . . . , rN , t) , (41)

∂t

All xc functionals perform much better than Hartree-

Fock. It is evident that the B3LYP functional gives the where the time-dependent Hamiltonian is defined as

best overall results, with accuracies that come close to

the requirements for predicting chemical reactions (the Ĥ(t) = T̂ + V̂ (t) + Ŵ . (42)

so-called “chemical accuracy” of 1 kcal/mol).

In solids, hybrid functionals such as B3LYP perform The time-dependent Hamiltonian has the same kinetic-

less well, due to the fact that they do not reduce to the energy and electron-electron interaction parts T̂ and Ŵ

exact homogeneous electron gas limit [29]. A detailed as the static Hamiltonian (2), but it features an external

assessment of the performance of modern density func- potential operator that is explicitly time-dependent:

tionals for bulk solids was given by Czonka et al. [30]. N

Generally speaking, GGA functionals do not improve the

X

V̂ (t) = v(rj , t) . (43)

lattice constants in nonmolecular solids obtained with j=1

LDA (which are already very good!): while LDA system-

atically underestimates lattice constants, GGA overesti- The time-dependent Schrödinger equation (41) for-

mates them. Vice versa, bulk moduli and phonon fre- mally represents an initial-value problem. We define a

quencies are typically overestimated by LDA and under- time t0 as our initial time (often, t0 = 0), and we start

estimated by GGA. This clearly affects many properties with a given initial many-body wave function of the sys-

of solids which are volume-dependent such as their mag- tem, Ψ(t0 ) ≡ Ψ0 (notice that this is not necessarily the

netic behavior. Some typical results for lattice constants ground state). This state is then propagated forward in

are given in Table II. time, describing how the system evolves under the influ-

A particular class of hybrid functionals, called range- ence of the time-dependent potential v(r, t). In many sit-

separated hybrids, has attracted much interest lately [33]. uations of practical interest, the time-dependent single-

The basic idea is to separate the Coulomb interaction into particle potential can be written as

a short-range (SR) and a long-range (LR) part:

v(r, t) = v0 (r) + θ(t − t0 )v1 (r, t) , (44)

1 f (µ|r − r′ |) 1 − f (µ|r − r′ |)

= + , (39)

|r − r′ | |r − r′ | |r − r′ | i.e., the potential is static and equal to v0 until time t0

when an explicitly time-dependent additional potential

where the function f has the properties f (µx → 0) = 1

v1 (t) is switched on.

and f (µx → ∞) = 0. Common examples are f (µx) =

The time-dependent wave function allows us to calcu-

e−µx and f (µx) = erfc(µx). The separation parameter µ

late whatever observable we may be interested in,

is determined either empirically [34–38] or using physical

arguments [33, 39]. The resulting range-separated hybrid O(t) = hΨ(t)|Ô|Ψ(t)i. (45)

xc functional then has the following generic form:

Here, O(t) is the time-dependent expectation value of the

Exc = ExSR−DFA + ExLR−HF + EcDFA , (40)

Hermitian operator Ô corresponding to a quantum me-

where DFA stands for any standard density-functional chanical observable. Two key quantities for TDDFT are

7

t t0 t t0

t t0

t t0

FIG. 2. First scenario of time evolution: the external po- FIG. 3. Second scenario of time evolution: the system starts

tential is static, but the system starts with a nonequilibrium from the ground state and evolves under a time-dependent

initial state. The density then oscillates back and forth. external potential that is switched on at the initial time t0 .

and j(r, t). They can be defined via the one-particle den- TDDFT will allow us to describe both dynamical sce-

sity operator and current density operator, narios formally exactly for arbitrary many-body systems.

To do this we will derive a dynamical version of the Kohn-

N

X Sham equations, which will allow us to carry out real-

n̂(r) = δ(r − ri ) (46) time propagations of quantum systems, starting from ar-

i=1 bitrary initial states and under the influence of arbitrary

N

X time-dependent potentials. We will derive the formal

ĵ(r) = [∇i δ(r − ri ) + δ(r − ri )∇i ] (47) framework of TDDFT in Section IV, and we will discuss

i=1 practical aspects and applications in Section V.

so that n(r, t) = hΨ(t)|n̂(r)|Ψ(t)i and similar for j(r, t). Of particular importance are situations in which the

A connection between density and current density is pro- external time-dependent potential can be considered a

vided by the continuity equation, weak perturbation. Very often one is interested in the

∂ first-order response of the system to a perturbation,

i n(r, t) = −∇ · j(r, t) . (48) because many spectroscopic techniques are used this

∂t

regime. In particular, the linear response of a material

There are many different types of quantum mechanical is directly related to its spectrum of excitations. As we

time evolution that are of practical interest. Many of will see in Sections VI and VII, TDDFT in the linear-

them belong to one of the following two generic scenarios. response regime is a very powerful approach to calculate

First scenario. Consider a system that starts from a excitation energies and optical spectra. In fact, this is

nonequilibrium initial state, and then freely evolves in where at present the majority of TDDFT applications

a static potential. A simple one-dimensional example is are carried out at present.

illustrated in Fig. 2: at the initial time t0 , the density has

an asymmetric shape which clearly does not come from

an eigenstate of the square-well potential. The density IV. THE FORMALISM OF TDDFT

is then “released” and starts to oscillate back and forth,

while the square well potential remains static [40].

This kind of free time evolution occurs in practice when A. The Runge-Gross theorem

the system is subject to a sudden switching or a short

“kick” at the initial time, and is then left to itself. For The foundation of ground-state DFT is the Hohenberg-

example, charge-density oscillations that are triggered in Kohn theorem, which we discussed in Section II B. The

this way play an important role in the field of “plasmon- unique 1:1 correspondence between ground-state densi-

ics” [41]. ties and potentials makes it possible to construct den-

Second scenario. Consider now a system that is ini- sity functionals in a meaningful way, and to deter-

tially in the ground state, and is then subject to a time- mine ground-state properties in principle exactly via self-

dependent potential that is switched on at time t0 . This consistent solution of the Kohn-Sham equation.

is illustrated in Fig. 3 for a square well potential that is For the time-dependent case we would like a similar

“shaken” by superimposing it with a time-dependent lin- rigorous formal foundation. But the situation is different

ear potential, which again leads to an oscillating density. from the ground state, in two important ways. First,

For example, this scenario takes place if an atom or in the time-dependent case we do not have a variational

molecule is hit by a strong laser pulse: the wave func- minimum principle. Secondly, the Schrödinger equation

tion is driven by the external field and gets “shaken up”, (41) is an initial-value problem, so whatever we will prove

which can then lead to ionization. has to be done with a given initial state in mind.

8

å j (r, t )

2

ê- + vs [n](r, t )új j (r, t ) = i j j (r, t ) = n(r, t )

Runge and Gross in 1984 [9]. They proved that if two N - ë 2 û ¶t j

j

electron systems start from the same initial state, but are

subject to two different time-dependent potentials, their Density n(r¢, t ¢) over all space and times t¢ £ t (initial value problem)

respective time-dependent densities will be different.

We consider two time-dependent potentials to be dif-

ferent if their difference is more than just a time-

dependent constant, n(r, t ¢)

t0 t1

for t > t0 . Otherwise they would give rise to two wave Y0 , F 0 vs [n, Y0 , F 0 ](r, t )

functions that differ only by a phase factor e−iα(t) , where

dα(t)/dt = c(t), as can easily be shown. Such purely FIG. 4. The time-dependent Kohn-Sham equation determines

time-dependent phase factors cancel out when one forms the time-dependent density self-consistently between the ini-

expectation values of operators using Eq. (45). tial time t0 and some final time t1 . The xc potential at time

The Runge-Gross theorem applies to potentials that t depends on densities at times t′ ≤ t, as well as on the initial

can be expanded in a Taylor series about the initial time: states of the interacting and of the Kohn-Sham system.

∞

X vk (r)

v(r, t) = (t − t0 )k . (50) time-dependent density, n(r, t), can be calculated from

k! a noninteracting system with N single-particle orbitals:

k=0

N

For such potentials, the following unique 1:1 correspon- X

dence can be proven: n(r, t) = |ϕj (r, t)|2 . (54)

j=1

unique 1:1

v(r, t) ✛ ✲ n(r, t) . (51) The orbitals ϕj (r, t) satisfy the time-dependent Kohn-

fixed Ψ0

Sham equation:

The proof proceeds in two steps. In the first step it is es-

∇2

tablished that different potentials produce different cur- ∂

i ϕj (r, t) = − + vs (r, t) ϕj (r, t) , (55)

rent densities, infinitesimally later than the initial time ∂t 2

t0 . One then goes on to show that if the current densities

are different, the densities must be different as well; to where the time-dependent effective potential is given by

prove this, the continuity equation (48) is used.

vs [n, Ψ0 , Φ0 ](r, t) = v(r, t)+ vH (r, t)+ vxc [n, Ψ0 , Φ0 ](r, t).

Just like in ground-state DFT, the unique 1:1 corre- (56)

spondence (51) allows us to write the potential as a func- Here, v(r, t) is the time-dependent external potential,

tional of the density: which we assume to have the form (44). The time-

dependent Hartree potential,

v(r, t) = v[n, Ψ0 ](r, t) . (52)

n(r′ , t)

Z

Notice the formal dependence on the initial state. How- vH (r, t) = d3 r′ , (57)

|r − r′ |

ever, this dependence goes away if the system starts from

the ground state, i.e., Ψ0 = Ψgs : the Hohenberg-Kohn depends on the instantaneous time-dependent density

theorem then tells us that Ψgs [n] is a functional of the only. The time-dependent xc potential formally has a

density, and v(r, t) can be thus written as a functional of functional dependence on the density, the initial many-

the density only. body state Ψ0 of the exact interacting system, and the

Since the potential can be written as a functional of initial state of the Kohn-Sham system Φ0 . This is

the density, the time-dependent Hamiltonian becomes a schematically illustrated in Fig. 4.

density functional as well, and hence the time-dependent

wave function and all observables:

C. Discussion: beyond Runge-Gross

O(t) = hΨ[n, Ψ0 ](t)|Ô|Ψ[n, Ψ0 ](t)i = O[n, Ψ0 ](t) . (53)

The Runge-Gross theorem in and by itself is sufficient

to serve as the fundamental formal basis of TDDFT.

B. Time-dependent Kohn-Sham formalism However, there are some subtle questions that it leaves

unanswered and some situations that are not covered by

The Kohn-Sham formalism (see Section II C) has been it. Extending the Runge-Gross theorem, or coming up

tremendously successful in ground-state DFT. Its time- with alternative proofs, has therefore been an area of

dependent counterpart looks very similar. The exact significant research activity.

9

less interested in the formal details of TDDFT, and more

interested in practical aspects. n(t )

Density

1. v-representability and the van Leeuwen theorem v(t ) given

lowing: given a well-behaved (i.e., continuous R and not

singular) mathematical function n(r), with d3 rn(r) =

N , can one always find a potential v0 (r) where this System 2: w (r r )

n(r) is a ground-state density? This is known as the

v-representability question; one distinguishes the inter- n(t )

Density

acting and the noninteracting v-representability problem,

depending on whether the given density is to be repro-

v ((t ) uniquely

duced in the physical (interacting) or in the Kohn-Sham determined

(noninteracting) system.

Why is v-representability an important issue? If there

exist density functions that are not v-representable (VR), FIG. 5. The van Leeuwen theorem states that a time-

then the domain of the functional Ev0 [n] would be ill de- dependent density n(t) coming from a many-body system

fined, and one would run into formal problems in defin- with interaction w(r − r′ ) and potential v(r, t) can be repro-

ing functional derivatives such as in Eq. (21). The v- duced in a system with different interaction, w′ (r − r′ ) and

representability problem in DFT is still not fully solved, potential v ′ (r, t). The potential v ′ is uniquely determined.

but at least we do know that all density functions on lat-

tice systems are VR [42] (ensemble-VR, to be precise).

Fortunately, it turns out that the v-representability prob- many-body systems with different particle-particle inter-

lem in ground-state DFT can be circumvented in an ele- actions, w(r−r′ ) (system 1) and w′ (r−r′ ) (system 2), see

gant way with the so-called constrained search formalism Fig. 5. If a time-dependent density n(r, t) is produced by

[43, 44], which is, essentially, a clever reformulation of the an external potential v(r, t) in system 1 (starting from a

variational minimum principle as a search over antisym- given initial state), then one can uniquely construct the

metric N -particle wave functions, so that potential v ′ (r, t) that produces the same density in sys-

tem 2 (the choice of initial state in system 2 is unique,

Ev0 [n] = minΨ→n hΨ|T̂ + V̂0 + Ŵ |Ψi. (58) too). There are some restrictions on the admissible densi-

ties: they must possess a Taylor expansion in t about the

For TDDFT the situation is different, due to a fun- initial time (we denote such densities as t-TE). Below,

damental difference between the ground-state problem we show that this assumption can be problematic.

and the time-dependent problem: rather than finding a The van Leeuwen theorem has two important special

ground state, TDDFT describes the time-propagation of cases. The first is that of w = w′ , i.e., the two systems

many-body systems under the influence of external po- are identical. It turns out that in this way one gains

tentials. Due to the central role the external potential an alternative proof of the Runge-Gross theorem. The

plays, the v-representability problem [i.e., whether there second case is w′ = 0, i.e., the second system is noninter-

exists a v(r, t) for every n(r, t)] seems unavoidable. acting. This establishes noninteracting v-representability

TDDFT is not formulated on the basis of a variational in TDDFT, and hence provides formal justification of the

minimum principle, since there is no quantity equivalent time-dependent Kohn-Sham approach.

to the role of energy in time-dependent systems. In-

stead, it is possible to formulate TDDFT via a stationary-

action principle [45–47]. However, the uniqueness of

the stationary-action point remains unproven. A rig- 2. Non-Taylor-expandable densities

orous time-dependent version of the constrained-search

approach does not exist, despite some attempts [48, 49]. The van Leeuwen theorem shows that for t-TE densi-

Some progress has been made with the time-dependent ties, one can always construct the corresponding t-TE po-

v-representability problem for lattice systems [50]. In- tential for the TDKS system. However, there is a subtle

terestingly, in this case it can happen very easily that difference between the domain of the van Leeuwen the-

perfectly well-behaved lattice densities are not VR, for orem and the Runge-Gross theorem, as the latter only

well-understood reasons [51]. requires the external potentials to be t-TE [Eq. (50)],

The van Leeuwen theorem [52] made an important con- but not the densities. The van Leeuwen theorem does

tribution towards the resolution of the v-representability not apply to non-t-TE densities, which are allowed by

problem in TDDFT. It makes a statement about two the Runge-Gross theorem. Such densities are commonly

10

t=0.1

pose any threat. However, it turns out [53, 54] that the t=0.2

t=0.5

densities of most real world systems can become non-t- 0.8 t=1

TE, including atoms, molecules, and solids!

In the usual non-relativistic quantum mechanical de- 0.6

0.4

diverging Coulomb potential, and the densities always

have cusps at the positions of nuclei [55]. The dynam- 0.2

ics of the system, including the time-dependent density,

is determined by the time evolution operator Û (t, t0 ), 0

which in turn follows from the Hamiltonian Ĥ(t). In -3 -2 -1 0 1 2 3

x(a.u.)

the presence of space-non-analytic features such as cusps,

time-non-analyticities appear because of the kinetic en- 1 t=0

t=0.1

ergy operator T̂ , which is a differential operator in space. t=0.2

t=0.5

Thus, the time-dependent density can become non-t-TE. 0.8 t=1

A striking example [53] demonstrating the difference

between the exact density and the t-TE density is shown 0.6

0.4

applying the t-TE time-evolution operator on the initial

state). At the initial time, a density with a cusp is pre-

0.2

pared, and then allowed to freely evolve in time. The

upper panel of Fig. 6 shows that the density rapidly 0

becomes smooth and spreads out. By contrast, if one -3 -2 -1 0 1 2 3

x(a.u.)

attempts to find the time evolution by using a Taylor

expansion, the density does not move at all!

We emphasize that although the Runge-Gross theo- FIG. 6. Upper panel: time-dependent density of a 1D sys-

rem is explicitly formulated for t-TE densities, the origi- tem with initial state ψ(x) = exp(−|x|) propagating with no

nal proof remains valid despite the existence of non-t-TE external potential. Lower panel: using a Taylor expansion

densities [54]. Thus, the foundations of TDDFT remain in time, the initial density remains stationary. This wrong

sound. behavior is due to the nonanalyticity of the density.

3. Fixed-point proofs the potential, denoted as v1 . Ref. [56] proves that under

mild restrictions, v0 = v1 , showing the mutual correspon-

Recent work on the v-representability problem and dence between the density and the potential. The proof

related questions focuses on developing so-called fixed- is strengthened by recent numerical simulations [57]. The

point proofs [56, 57], where the previous limitation of fixed-point proofs apply to densities confined within a fi-

t-TE is lifted. The van Leeuwen theorem provides a way nite (but arbitrarily large) space region, and the cases

of constructing the time-dependent external potential for of density cusps are included in a limiting sense. It is

a given density, if the density is t-TE; if applied on non- not clear as of now whether these restrictions are general

t-TE densities, the constructed potential does not cor- enough for the v-representability problem.

respond to the exact density, but in turn reproduces the

t-TE density [54]. The fixed-point proofs [56, 57] thus fo-

cus on explicitly showing the one-to-one correspondence 4. Vector potentials and time-dependent current-DFT

between the potential and the density. The proof starts

from the equation of motion of the density [52]: TDDFT applies to electronic many-body systems in

2

∂ n(r, t) the presence of time-dependent scalar potentials. But

− ∇ · [n(r, t)∇v(r, t)] = q(r, t). (59) there are important classes of time-dependent processes

∂t2 that are not included, namely, many-body systems in

The density and the quantity q can be seen as function- time-dependent magnetic fields or under the influence of

als of the potential, and thus Eq. (59) uniquely maps electromagnetic waves. This is obviously a very severe

a potential v0 to q[v0 ], with the density n[v0 , Ψ0 ] deter- omission, because this means that, strictly speaking, this

mined by v0 and the initial wave function Ψ0 . In another precludes discussing the interaction between light and

perspective, Eq. (59) can also be seen as a differential matter! In practice, we can often get around this restric-

equation for the potential, when n and q are given. If this tion and treat electromagnetic fields in dipole approxima-

given density is chosen to coincide with the initial den- tion, so that TDDFT is applicable. But in the general

sity of the system and with its first-order time-derivative, case, to deal with vector potentials of the form A(r, t)

and q is chosen to be q[v0 ], Eq. (59) can be solved for we need a theory that goes beyond TDDFT.

11

In general, a system can be under the influence of both this would be relativistically small. The gauge-invariant

a scalar and a vector potential, v(r, t) and A(r, t). The physical current density is given by

many-body Hamiltonian is then given by

N

1X ∗

N j(r, t) = n(r, t)As (r, t) + ℑ ϕj (r, t)∇ϕj (r, t) .

( 2 )

X 1 ∇j i j=1

Ĥ(t) = + A(rj , t) + v(rj , t) + Ŵ . (60)

j=1

2 i (68)

Let us summarize the key points of TDCDFT:

The time-dependent many-body wave function associ-

ated with Ĥ(t) determines the density n(r, t) and the 1. TDCDFT overcomes formal limitations of TDDFT,

current density j(r, t). It is important to keep in mind allowing treatment of electromagnetic waves and

that the current density, like any general vector field, has general vector potentials and time-varying mag-

a longitudinal and a transverse component, netic fields. However, electromagnetic waves are

usually treated in dipole approximation, so one

j(r, t) = jL (r, t) + jT (r, t) . (61) rarely makes use of TDCDFT in this way.

The longitudinal current density is related to the density 2. The Runge-Gross theorem of TDDFT has been

via the continuity equation: proved for finite systems, where the density van-

ishes at infinity. However, it also works for periodic

∂ systems [62], provided the external potential is also

n(r, t) = −∇ · jL (r, t) , (62)

∂t periodic. The Runge-Gross theorem does not ap-

but the transverse component jT (r, t) is not determined ply when a uniform homogeneous field acts on a

by n. Hence, current densities are, in general, not VR periodic system. This case, however, is formally

[58]: if j(r, t) = jL (r, t) + jT (r, t) comes from a potential included in TDCDFT [60].

v(r, t), then j′ (r, t) = jL (r, t)+j′T (r, t) (same longitudinal 3. TDCDFT can be very useful in situations that

but different transverse component) cannot come from could, in principle, be fully described with TDDFT;

a potential v ′ (r, t), since this would violate the Runge- using the current as basic variable, rather than the

Gross theorem. Hence, we need the full mapping density, can make it easier to develop approxima-

tions for dynamical xc effects [63, 64].

(v, A) ↔ (n, j) . (63)

V. PRACTICAL ASPECTS

transformation:

∂

v(r, t) → v(r, t) − Λ(r, t) (64) To apply TDDFT in practice requires the following

∂t considerations:

A(r, t) → A(r, t) + ∇Λ(r, t) , (65)

• a suitable approximation for the time-dependent xc

where Λ(r, t) is an arbitrary (but well-behaved) gauge

potential needs to be found;

function which vanishes at the initial time. Often, one

chooses the gauge function in such a way that the scalar • the time-dependent Kohn-Sham equations need to

potential vanishes. be solved numerically;

Ghosh and Dhara [59] were the first to give a formal

proof of time-dependent current-DFT (TDCDFT). More • the physical observables of interest need to be ob-

recently, an alternative existence proof of TDCDFT, in tained from the time-dependent density.

the spirit of the van Leeuwen theorem, was provided by

Vignale [60]. TDCDFT on lattice systems was discussed Each of these points has its own challenges. We shall

by Tokatly [61]. The time-dependent Kohn-Sham equa- now address them individually, including some examples.

tion in TDCDFT becomes

( 2 )

∂ 1 ∇ A. The time-dependent xc potential

i ϕj (r, t) = + As (r, t) + vs (r, t) ϕj (r, t) ,

∂t 2 i

(66) As we said in Section IV B, the time-dependent xc po-

where the effective scalar potential, as before, is given by tential is formally a functional of the time-dependent den-

Eq. (56), and the effective vector potential is sity as well as the initial states, vxc [n, Ψ0 , Φ0 ](r, t). In

practice, one is usually interested in situations where the

As (r, t) = A(r, t) + Axc (r, t) . (67) system is initially in the ground state. If this is the case,

things simplify considerably: thanks to the Hohenberg-

Notice that the effective vector potential does not con- Kohn theorem of ground-state DFT, the initial states

tain a Hartree-like term due to induced currents, since become functionals of the initial (ground-state) density,

12

and the xc functional can be written as a density func- quantum mechanical features such as atomic shell struc-

tional only, vxc [n](r, t). ture, covalent molecular bonds, or lone pairs. Such in-

However, the density-dependence of the xc potential formation can be gained from a convenient visualization

is complicated and nonlocal: the xc potential at space- tool known as the time-dependent electron localization

time point (r, t) depends on densities at all other points in function (TDELF) [72]. The TDELF is defined as a pos-

space and at all previous times, n(r′ , t′ ), where t′ ≤ t (the itive quantity with a magnitude between zero and one:

potential cannot depend on densities in the future—this

would violate the fundamental principle of causality). 1

fELF (r, t) = . (71)

The most widely used approximation for the xc poten- 1 + [Dσ (r, t)/Dσ0 (r, t)]2

tial is the adiabatic approximation:

The quantity

A gs

vxc (r, t) = vxc [n0 ](r)|n0 (r)=n(r,t) , (69)

|∇nσ (r, t)|2 |jσ (r, t)|2

gs Dσ (r, t) = τσ (r, t) − − (72)

where vxc ,the ground-state xc potential defined in Eq. 8nσ (r, t) 2nσ (r, t)

(21), is evaluated at the instantaneous time-dependent

density. Eq. (69) becomes exact for an infinitely slowly is a measure of the probability of finding an electron in

varying system which is in its ground state for any time. the vicinity of another electron of the same spin σ at

In practice, this is of course not the case (unless one (r, t). Clearly, Dσ (r, t) is not an explicit density func-

considers a time-dependent system which just sits there tional, but it is expressed in terms of the density, the

in its ground state, doing nothing). current, and the orbitals via the kinetic-energy density

τσ (r, t) = 21 N 2 0

P σ

One of the most important questions in TDDFT is j=1 |∇ϕjσ (r, t)| . Dσ in Eq. (71) is given

under what circumstances the adiabatic approximation by the kinetic-energy density of the homogeneous elec-

works well. Numerical studies [65–67] demonstrate that tron liquid:

the adiabatic approximation may break down if the sys-

tem undergoes very rapid changes, but it turns out that 3

Dσ0 (r, t) = (6π 2 )3/2 n5/3 h

σ (r, t) = τσ (r, t) . (73)

the adiabatic approximation still works surprisingly well 10

in many cases. This will be further addressed below when The time propagation is unitary, so the total norm is

we discuss the calculation of excitation energies. conserved; but to describe ionization or charge transfer

As of today, very few applications of TDDFT have processes, it is often of interest to obtain the number of

been carried out with nonadiabatic, explicitly memory- electrons that escape from a given spatial region V:

dependent xc functionals [68–71]. Due to its simplic-

ity, the overwhelming majority of time-dependent Kohn-

Z

Sham calculations use the adiabatic LDA (ALDA), Nesc (t) = N − d3 n(r, t) . (74)

V

ALDA LDA

vxc (r, t) = vxc (n(r, t)) , (70) Here, V can be thought of as a “box” that surrounds

the entire system (in case we wish to calculate ionization

or any adiabatic GGA defined in a similar way, by re- rates of atoms or molecules), or it could be a part of a

placing the ground-state density with the instantaneous larger molecule or part of a unit cell of a periodic solid.

time-dependent density. Another easy class of observables are moments of the

density, such as the dipole moment:

B. Observables Z

d(t) = d3 r rn(r, t) . (75)

In Section IV A we showed that all physical observables

are formally functionals of the time-dependent density, The dipole moment can be considered directly, i.e., in

see Eq. (53). TDDFT gives, in principle, the exact time- real time, to study the behavior of charge-density oscil-

dependent density n(r, t), and all quantities of interest lations. Alternatively, it can be Fourier transformed to

must be obtained from it. Some observables are easily yield the dipole power spectrum |d(ω)|2 or related observ-

calculated in this way, but other are not. We will now able quantities such as the photoabsorption cross section.

give examples of both kinds. Higher moments of the density, such as the quadrupole

moment, can be calculated just as easily, but are less

frequently considered.

1. Easy observables

The easiest observable is the density itself, which shows 2. Difficult observables

how electrons move during any time-dependent process.

This is certainly useful for visualizing molecular geome- Equation (74) gives the total number of escaped elec-

tries or structural changes during chemical reactions or trons, which in general can be nonintegral. For in-

photoinduced processes, but does not reveal important stance, if we consider an atom in a laser field, a value of

13

Nesc = 0.5 would indicate that on average half an elec- for given initial and final many-body states Ψi and Ψf .

tron has been removed. In reality there are of course no To get the S-matrix from the density, a cumbersome im-

“half-electrons”, so we have to interpret this result in a plicit read-out procedure was proposed [79].

probabilistic sense: it could for instance mean that there Momentum distributions. Ion recoil momenta are of

is 50% probability that the atom is singly ionized, and great interest in high-intense field or scattering experi-

50% probability that it is not ionized; other scenarios, ments. The problem is formally similar to the problem

involving double ionization, are also possible. The prob- of calculating ion probabilities from the density, and in

abilities to find an atom or molecule in a certain charge principle requires the full wave function in momentum

state +m can be defined as follows [73]: space. The Kohn-Sham momentum distributions can be

Z Z taken as approximation, without formal justification [80].

P (t) = d r1 . . . d3 rN |Ψ(r1 , . . . , rN , t)|2

0 3

(76) Transition density matrix. The transition density ma-

V V

trix is a quantity that is defined in the linear response

Z Z Z regime. As the name indicates, it refers to a specific

+1 3 3

P (t) = d r1 d r2 . . . d3 rN |Ψ(r1 , . . . , rN , t)|2 (77) excitation of the system (typically, a large molecular sys-

V V V tem), and maps the distribution and coherences of the

excited electron and the associated hole. In particular,

and similar for all other P +m (t). Here V denotes all the transition density matrix is useful to visualize exci-

space outside the integration box V surrounding the sys- tonic effects. There is no easy way to obtain it directly

tem. The ion probabilities are defined in terms of the from the density; the best we can do is to construct the

full many-body wave function Ψ(t), which is a density transition density matrix from Kohn-Sham orbitals [81].

functional according to the Runge-Gross theorem; but it All the above examples have in common that they are

is not possible to extract the ion probabilities P +m (t) explicit expressions of the many-body wave function, or

directly from the density in an elementary way. of the N -body density matrix, but can only be implicitly

Since the full wave function is prohibitively expensive expressed as density functionals. One can get approxi-

to deal with, a pragmatic solution is to replace Ψ(t) by mate results by replacing the full many-body wave func-

the Kohn-Sham Slater determinant Φ(t), in spite of the tion with the Kohn-Sham Slater determinant Φ(t), but

fact that the latter has no rigorous physical meaning. there is no guarantee that this will give good results.

One then obtains the Kohn-Sham ion probabilities

Ps0 (t) = N1 (t)N2 (t) . . . NN (t) (78) C. Applications

N

X

Ps+1 (t) =

N1 (t) . . . Nj−1 (t) 1 − Nj (t)

Real-time TDDFT has been implemented in several

j=1

computer codes, most notably the open-source code

×Nj+1 (t) . . . NN (t) (79) octopus [82, 83]. A TDDFT code must deal with two ba-

and similar for all other Ps+m (t), where sic numerical tasks: (i) The Kohn-Sham orbitals of the

Z system, and its density, must be represented in space.

This can be done either with a suitable basis, or on a

Nj (t) = d3 r|ϕj (r, t)|2 . (80)

spatial grid using finite-element or finite-difference dis-

V cretization schemes (octopus uses the latter). (ii) Time

The Kohn-Sham ion probabilities are easily obtained must be discretized as well, and the time-dependent

from the orbitals; but apart from certain limiting cases Kohn-Sham equations are propagated forward in time,

[73], they are have no rigorous physical meaning [74, 75]. step by step, ensuring norm conservation.

Here are some other examples of difficult observables: Let us say a few words about the time propagation.

Photoelectron spectra. The photoelectron kinetic en- Suppose we know the Kohn-Sham orbitals up until some

ergy distribution spectrum is formally defined as time τn . The orbitals at the next time step, τn+1 =

τn + ∆τ , can then formally be written as

N

X

P (E)dE = lim |hΨkE |Ψ(t)i|2 dE , (81) ϕj (τn + ∆τ ) = Û (τn + ∆τ, τn )ϕj (τn ) , (83)

t→∞

k=1

where Û (τn +∆τ, τn ) is the time evolution operator which

where |ΨkE i is a many-body eigenstate with k electron in propagates the orbitals one time step ∆τ forward. If ∆τ

the continuum and total kinetic energy E of the contin- is sufficiently small, we can approximate Û by

uum electrons. There are approximate ways of calculat-

ing photoelectron spectra from the density or from the Û (τn + ∆τ, τn ) ≈ e−iĤs (τn +∆τ /2)∆τ , (84)

Kohn-Sham orbitals [76–78].

State-to-state transition probabilities. The S-matrix where Hs (τn + ∆τ /2) is the time-dependent Kohn-Sham

describes the transition between two states: Hamiltonian evaluated midway between the two time

steps (in practice, this requires a so-called predictor-

Si,f = lim hΨf |Ψ(t)i , (82) corrector scheme [1]). The time propagation (83) can

t→∞

14

Time (a.u.)

Intensity (a.u.)

Energy (eV)

molecule. Top: time-dependent dipole moment d(t) induced

by an initial “kick”. Bottom: dipole spectrum, obtained by FIG. 8. Two snapshots of the time-dependent electron local-

Fourier transforming d(t) (full line), compared with the spec- ization function (TDELF) for a CO2 molecule, excited by

trum obtained from linear-response TDDFT (thin line). a laser pulse of photon energy 20 eV and intensity 1.2 ×

1015 W/cm2 . Insets: density isosurfaces.

dipole moment, agrees well with a spectrum that is ob-

ample is the Crank-Nicholson algorithm:

tained from linear-response TDDFT (we will discuss this

approach in the following Section). Both spectra, in turn,

1 − iĤs ∆τ /2 agree well with experiment [93].

e−iĤs ∆τ ≈ , (85)

1 + iĤs ∆τ /2 The second class of applications is in the nonlinear

regime, and deals with systems that are subject to strong

which is correct to order (∆τ )2 and unitary (hence, the excitations such as high-intensity laser pulses or collisions

norm of the wave functions is conserved). This converts with fast, highly charged ionic projectiles. The response

the time-dependent Kohn-Sham equations into a set of following such excitations can be highly nonlinear and

linear equations that can be numerically solved. far beyond any treatment using perturbative methods.

The applications of real-time TDDFT can be roughly Propagation of the time-dependent Kohn-Sham equa-

divided into two categories, related to the two scenarios tions yields the response to all orders, in principle ex-

we discussed in Section III. actly, including collective many-body effects. Quantities

In the first class of applications, the system is initially of interest include easy observables such as total ioniza-

prepared in a nonequilibrium state through a sudden tion yields and high-harmonic generation spectra, and

switching or a short impulsive excitation, and then al- difficult observables such as photoelectron spectra, ion

lowed to propagate freely in time [85–87]. The initial probabilities, or momentum distributions.

perturbation is kept weak in order to avoid any non- Figure 8 shows an example. A CO2 molecule is hit with

linear effects, but it is spectrally broad and hence trig- a very short, high-intensity laser pulse which deposits a

gers a dynamical behavior of the system in which essen- large amount of excitation energy in a very short time.

tially the entire range of excitations participates. The The snapshot at t = 10.6 a.u. (1 a.u. equals 24 attosec-

time-dependent dipole moment d(t), Eq. (75), is cal- onds) shows how a packet of density flies off, and the

culated over a certain time span, and Fourier transfor- remaining density is strongly distorted. The TDELF,

mation yields the optical spectrum of the system. The Eq. (71), illustrates how the electronic orbitals have be-

time-propagation method has certain advantages espe- come extremely diffuse, and the bonds are essentially de-

cially for large systems [88–91] and metallic clusters [92], stroyed, which will cause the molecule to break up.

but is less frequently used for low-lying excitations of TDDFT calculations for strong excitations have been

smaller molecules. Below, in Section VI, we will discuss carried out over the past two decades for a variety of

an alternative way of calculating excitation energies. atomic and molecular systems [74, 75, 80, 94–99] (see

Figure 7 shows an example of such a calculation for [100] for a review). An intriguing question is whether

the CO2 molecule. The optical absorption spectrum, it is possible to design the excitation (i.e., the laser in-

obtained by Fourier transforming the time-dependent tensity, pulse shape, and spectral composition) in such as

15

way that a specific control goal can be achieved. The for- The step function θ(t − t′ ) ensures that the response is

mal framework of TDDFT and optimal control has been causal, i.e., the response comes after the perturbation.

worked out [101, 102], but some of the more interesting Equation (88) shows that the response function is ob-

control goals may be difficult to achieve with standard tained from the many-body ground state Ψgs , involving

(adiabatic) TDDFT approaches [103–107]. a commutator of density operators (in interaction rep-

resentation). Hence, via the Hohenberg-Kohn theorem,

it is formally a functional of the ground-state density,

VI. TDDFT AND LINEAR RESPONSE χ[n0 ]. Usually, one is more interested in the frequency-

dependent response than in the real-time response:

A. Formalism Z

n1 (r, ω) = d3 r′ χ(r, r′ , ω)v1 (r′ , ω) . (89)

In many situations of practical interest, systems are

subjected to small perturbations and hence do not de-

The Fourier transform of the response function (88) can

viate strongly from their initial state. This happens in

be written in the following form, known as the Lehmann

most applications of spectroscopy, where the response to

representation [1, 18]:

a weak probe is used to determine the spectral proper-

ties of a system. In this case, it is not necessary to seek a ∞

′

X hΨgs |n̂(r)|Ψn ihΨn |n̂(r′ )|Ψgs i

fully-fledged solution of the time-dependent Schrödinger χ(r, r , ω) =

or Kohn-Sham equations (although this would yield the n=1

ω − Ωn + iη

desired information, too, as we have seen in Fig. 7). hΨgs |n̂(r′ )|Ψn ihΨn |n̂(r)|Ψgs i

Instead, one can use perturbation theory. The goal of − , (90)

ω + Ωn + iη

linear-response theory is to directly calculate the change

of a certain variable or observable to first order in the where the limit η → 0+ is understood. Here,

perturbation, without calculating the change of the wave

function. For us, the most important example is the lin- Ωn = En − E0 (91)

ear density response.

We consider the case where the system is initially in the is the nth excitation energy of the many-body system.

ground state and a time-dependent potential is switched This shows explicitly that the response function has poles

on at time t0 , see Eq. (44). Now, however, v1 (r, t) is at the exact excitation energies of the system. This

treated as a small perturbation. This perturbation will makes sense: if we apply a perturbation v1 (r, ω) whose

cause some (small) time-dependent changes in the sys- frequency matches one of the excitation energies, the re-

tem, and the density will become time-dependent. We sponse of the system is very large (we see a peak in the

expand it as follows: spectrum).

If we knew the response function χ of the many-body

n(r, t) = n0 (r) + n1 (r, t) + n2 (r, t) + . . . . (86) system, calculating the density response would be easy

and straightforward: all we have to do is evaluate ex-

Here, n0 is the ground-state density, n1 is the linear den-

pression (89). From the density response, spectroscopic

sity response (the first-order change in density induced

observables of interest can then be calculated. For in-

by the perturbation v1 ), n2 is the second-order density

stance, one often considers a monochromatic dipole field

response (quadratic in the perturbation v1 ), and there

along, say, the z direction,

will be higher-order terms which we have not explicitly

indicated. If the perturbation is small, the linear density v1 (r, t) = Ez sin(ωt) . (92)

response dominates over all higher-order terms in the ex-

pansion (86). On the other hand, if the perturbation is The dynamic dipole polarizability follows as

strong, a perturbation expansion may not even converge!

In that case it makes more sense to solve the Schrödinger 2

Z

(or Kohn-Sham) equations instead. Notice that all con- α(ω) = − d3 r zn1 (r, ω) , (93)

E

tributions

R 3 to the density response integrate to zero, e.g.,

d r n1 (r, t) = 0, due to norm conservation. and the photoabsorption cross section σ(ω) is given by

The linear density response can be formally written as

4πω

Z ∞ Z σ(ω) = ℑα(ω) . (94)

n1 (r, t) = dt ′

d3 r′ χ(r, t, r′ , t′ )v1 (r′ , t′ ) . (87) c

−∞

In TDDFT, the linear density response can be calculated,

Here, χ(r, r′ , t − t′ ) is the density-density response func- in principle exactly, as the response of the noninteracting

tion, defined as [1, 18] Kohn-Sham system to an effective perturbation [108]:

Z Z

′

(88) n1 (r, t) = dt d3 r′ χs (r, t, r′ , t′ )v1s (r′ , t′ ) . (95)

16

tion of the Kohn-Sham system. The effective perturba-

XZ Z

tion is given as the sum of the real external perturbation n1σ (r, t) = dt ′

d3 r′ χsσσ′ (r, t, r′ , t′ )v1sσ (r′ , t′ ) ,

plus the linearized Hartree and xc potentials: σ′

Z

n1 (r′ , t) (102)

vs1 (r, t) = v1 (r, t) + d3 r′ where the Kohn-Sham response function is diagonal in

|r − r′ | the spin index:

Z Z

+ dt′ d3 r′ fxc (r, t, r′ , t′ )n1 (r′ , t′ ) . (96) ∞

X

χsσσ′ (r, r′ , ω) = δσσ′ (fkσ − fjσ )

The so-called xc kernel is defined as the functional deriva- j,k=1

tive of the time-dependent xc potential with respect to ϕjσ (r)ϕ∗kσ (r)ϕ∗jσ (r′ )ϕkσ (r′ )

the time-dependent density, evaluated at the ground- × ,(103)

ω − ωjkσ + iη

state density:

and ωjkσ = εkσ − εjσ . The effective perturbation is

δvxc [n](r, t)

fxc (r, t, r′ , t′ ) = . (97)

δn(r′ , t′ ) n0 (r)

XZ

3 ′ 1

vs1σ (r, ω) = v1σ (r, ω) + d r

|r − r′ |

σ′

The effective perturbation (96) depends on the density

response, so the TDDFT response equation (95) has to +fxcσσ′ (r, r′ , ω) n1σ′ (r′ , ω) , (104)

be solved self-consistently. Again, we are usually more

interested in the frequency-dependent response, given by

featuring the spin-dependent xc kernel fxcσσ′ .

Z

n1 (r, ω) = d3 r′ χs (r, r′ , ω)v1s (r′ , ω) , (98)

B. How to calculate excitation energies

and

The excitation energies of a many-body system are de-

vs1 (r, ω) = v1 (r, ω) (99)

fined as the differences between the ground-state energy

1

Z

+ d r 3 ′

+ fxc (r, r′ , ω) n1 (r′ , ω) . E0 and the energies of higher-lying eigenstates, En , see

|r − r′ | Eq. (91). In other words, they are obtained by comparing

the energies of stationary states. Why, then, would one

The frequency-dependent xc kernel is the Fourier trans-

want to use a time-dependent approach such as TDDFT?

form of fxc (r, t, r′ , t′ ) with respect to (t − t′ ).

Isn’t that unnecessarily complicated?

The Kohn-Sham response function is given by

It helps to think of an excitation in a different way,

∞

X ϕj (r)ϕ∗k (r)ϕ∗j (r′ )ϕk (r′ ) namely, as a dynamical process where the system tran-

′ sitions between two eigenstates; the excitation energy

χs (r, r , ω) = (fk − fj ) ,

ω − ωjk + iη then corresponds to a characteristic frequency, which de-

j,k=1

(100) scribes the rearrangements of probability density during

where fj and fk are occupation numbers referring to the the transition process. In other words, each excitation

configuration of the Kohn-Sham ground state (1 for oc- corresponds to a characteristic eigenmode of the inter-

cupied and 0 for empty Kohn-Sham orbitals), and the acting N -electron system.

ωjk are defined as The concept of electronic eigenmodes has a familiar

analog in classical mechanics [109]. A system of s coupled

ωjk = εj − εk . (101) oscillators carrying out small oscillations is described by

the homogeneous linear system of equations

Thus, χs (r, r′ , ω) has poles at the excitation energies

of the noninteracting Kohn-Sham system. Naively, one s

X

might conclude from this that the TDDFT linear re- (kij − Ω2 mij )Aj = 0 , i = 1, . . . , s, (105)

sponse must be wrong, since it contains a response func- j=1

tion with the wrong pole structure (we pointed out above

that the exact response function has poles at the ex- where the matrices kij and mij determine the potential

act excitation energies Ωn ). The resolution to this ap- and kinetic energy of the system, respectively:

parent contradiction lies in the self-consistent nature of s

1X

the TDDFT response equation, which “cancels out” the U= kij qi qj (106)

wrong poles and restores the correct poles of the many- 2 ij

body system. s

1X

The TDDFT linear-response formalism can be gener- T = mij qi qj (107)

alized to a spin-dependent form. The response equation 2 ij

17

(the qj are generalized coordinates). Clearly, kij and mij accurate [110–112]. The eigenmodes can be calculated,

generalize the concept of spring constant and mass of a in principle exactly, using the so-called Casida equation

simple harmonic oscillator. The solutions of Eq. (105) [113]:

are obtained by finding the roots of the determinant, ! ! ! !

A K X −1 0 X

det|kij − Ω2 mij | = 0 . (108) =Ω , (114)

K A Y 0 1 Y

The s solutions Ω2α , α = 1, . . . , s, are the eigenfrequen-

cies of the system, and the associated eigenvectors Ajα where the matrix elements of A and K are given by

indicate the profile of the eigenmode, and can be used to Aiaσ,i′ a′ σ′ (ω) = δii′ δaa′ δσσ′ ωaiσ + Kiaσ,i′ a′ σ′ (ω) (115)

determine the normal modes of the system. Z Z

It turns out that calculating excitation energies with Kiaσ,i a σ (ω) = d r d3 r′ ϕ∗iσ (r)ϕaσ (r)

′ ′ ′

3

tions of a classical system. Starting point is the TDDFT × fHxcσσ′ (r, r′ , ω)ϕi′ σ′ (r′ )ϕ∗a′ σ′ (r′ ) (116)

response equation, Eq. (98), but without any external

perturbation: and i, i′ and a, a′ run over occupied and unoccupied

Kohn-Sham orbitals, respectively. A detailed derivation

of Eq. (114) can be found in Ref. [1].

Z Z

n1 (r, ω) = d3 r′ χs (r, r′ , ω) d3 r′′ fHxc (r′ , r′′ , ω)n1 (r′′ , ω) If one assumes that the Kohn-Sham orbitals are real

(109) and that the xc kernel is frequency-independent (more

where we define the combined Hartree-xc kernel as about this assumption in section VI D), it is possible to

fHxc (r, r′ , ω) = |r − r′ |−1 + fxc (r, r′ , ω). Equation (109) recast the Casida equation into the following form:

has the trivial solution n1 = 0 for all frequencies ω, but X h

2

at certain special frequencies Ω there are also nontrivial δii′ δaa′ δσσ′ (ωiaσ − Ω2 )

solutions where the density response is finite and self- i′ a′ σ′

sustained, despite the fact that there is no external per- √ i

+ 2 ωiaσ ωi′ a′ σ′ Kiaσ,i′ a′ σ′ Zi′ a′ σ′ = 0 . (117)

turbation. These frequencies correspond to the excita-

tion energies of the system, and n(r, Ω) is the profile of This equation can be viewed as the TDDFT counterpart

the associated electronic eigenmode. of the eigenvalue equation (105) for classical small oscil-

To illustrate how this works, consider the simple case lations. Hence, Eq. (117) yields the excitation energies

of two electrons in a two-level system with Kohn-Sham and eigenmodes of the given system.

orbitals ϕ1 (r) and ϕ2 (r), assumed to be real. Each level Eq. (114) mixes excitations and de-excitations (X and

is two-fold degenerate, and the lower level is doubly oc- Y, respectively). One may simplify Eq. (114) by setting

cupied. Dropping the infinitesimal iη, the Kohn-Sham the off-diagonal K matrix to zero, which decouples exci-

response function (100) then simplifies to tations and de-excitations. This so-called Tamm-Dancoff

approximation (TDA) is valid if the excitation frequen-

4ω21

χs (r, r′ , ω) = ′ ′

2 ϕ1 (r)ϕ2 (r)ϕ1 (r )ϕ2 (r ). (110)

cies are not close to zero, which is the case for molecules,

ω 2 − ω21 semiconductors, and insulators. The TDA often helps

We substitute this into Eq. (109), and after a few simple to compensate for deficiencies that arise because the xc

functionals are not exactly known and have to be ap-

manipulations we find the condition

proximated; the TDA can therefore be preferable over

ω 2 = ω21

2

+ 4ω21 K(ω) , (111) the full calculation (in the sense of getting qualitatively

correct results) in certain situations (e.g. triplet instabil-

where ities [114], conical intersections [115], and excitons [116]).

Z Z

K(ω) = d3 r d3 r′ ϕ1 (r)ϕ2 (r)fHxc (r, r′ , ω)ϕ1 (r′ )ϕ2 (r′ ).

C. Charge-transfer excitations

(112)

It is a simple exercise to repeat the above example using

the spin-dependent response formalism. Assuming that An important class of excitations are those in which

the ground state is not spin polarized (i.e., the spin-up charge physically moves from one region (the donor) to a

and spin-down orbitals are the same), one finds the fol- second region (the acceptor) which is spatially separated

lowing solutions for the eigenmodes: from the first. Such processes can occur in a wide range of

systems, such as in complexes of two or more molecules,

2

ω± 2

= ω21 + 2ω21 [Kσσ (ω) ± Kσσ̄ (ω)]. (113) or between different functional groups within the same

molecule. Unfortunately, the standard approximations

The plus sign represents a singlet excitation, and the mi- in TDDFT fail for charge-transfer excitations [117–119].

nus sign represents a triplet excitation. Consider the case where the donor and acceptor sub-

The simple examples for two-level systems are instruc- systems are separated by a large distance R. The min-

tive, but in practice turn out not to be quantitatively imum energy required to remove an electron from the

18

donor is given by the donor’s ionization potential Id . practice, will not change the number of poles, but just

When the electron attaches to the acceptor, some of shift them. To obtain double excitations, a frequency-

that energy is regained via the acceptor’s electron affinity dependent fxc (ω) is needed which will generate addi-

Aa . Once the electron has moved from donor to accep- tional solutions, since the Casida equation then becomes

tor the two systems feel the electrostatic interaction en- a nonlinear eigenvalue problem.

ergy −1/R of the induced electron–hole pair. The exact Thus, we can say the following about the adiabatic

charge-transfer energy is therefore approximation in TDDFT:

1 • The adiabatic approximation works well for those

Ωexact

ct = Id − Aa − . (118)

R excitations of the physical system for which a corre-

Now let us compare this with TDDFT. To make our point spondence to a single excitation in the Kohn-Sham

it is sufficient to consider the two-level approximation, system exists. The Casida equation then shifts the

Eq. (111). After linearization, we obtain Kohn-Sham excitations towards the true single ex-

Z Z citations.

Ωct = εaL − εdH + 2 d3 r d3 r′ ϕaL (r)ϕdH (r) • The frequency dependence of fxc must kick in for

those excitations of the physical system that are

× fHxc (r, r′ , ω)ϕaL (r′ )ϕdH (r′ ) , (119) missing in the Kohn-Sham system, namely, double

where ϕdH (r) is the highest occupied donor orbital and or multiple excitations.

ϕaL (r) is the lowest unoccupied acceptor orbital, which

have exponentially vanishing overlap in the limit of large Several nonadiabatic TDDFT approaches for the de-

separation. Hence, the double integral in Eq. (119) be- scription of molecular double excitations have been ex-

comes zero (assuming that the xc kernel remains finite, plored in the literature. One of them is known as dressed

which is certainly the case for all standard approxima- TDDFT [128], where a frequency-dependent xc kernel is

tions), and TDDFT simply collapses to the difference explicitly constructed within a small subspace. Other

between the bare Kohn–Sham eigenvalues, nonadiabatic approaches are based on many-body the-

ory [129–132]. However, none of these approaches is

Ωct −→ εaL − εdH . (120) sufficiently straightforward to be part of mainstream

TDDFT.

This explains why TDDFT often drastically underesti-

mates charge-transfer excitations when conventional xc

functionals are used. Hybrid xc functionals [120, 121], in E. Periodic systems and long-range behavior

particular the range-separated hybrids of Section II E, of-

fer a solution to this problem, and have been successfully As seen from Eqs. (115) and (116), the Casida equa-

used to describe charge-transfer excitations in a variety tion is expressed in the space spanned by one-particle

of systems [122–124]. Kohn-Sham transitions [133]. Real-space kernels are suit-

able for calculations of finite systems such as atoms and

molecules. For periodic systems like solids, the momen-

D. Beyond the adiabatic approximation

tum space representation of the Hartree-xc kernel is more

convenient. In Section VII D we will use this approach

The exact excitation spectrum of a physical system is to describe the optical properties of insulating solids.

determined by the poles of the full response function χ, The real space representation of the kernel is related

Eq. (90). All of the excitation energies Ωn of the many- to the momentum space representation as

body system are, in principle, obtained by solving the

Casida equation (114). But it is found that within the 1 X X

adiabatic approximation for fxc , some of the excitations fHxcσσ′ (r, r′ , ω) = ei(q+G)·r

V

are missing [125–127]! The missing excitations turn out q∈FBZ G,G′

to be those that have the character of double (or mul- ′

× fHxcσσ′ (q, G, G′ , ω)e−i(q+G )·r , (121)

′

states, if expanded in a basis of Kohn-Sham Slater deter- where G, G′ are reciprocal lattice vectors. With Eq.

minants, contain dominant contributions of doubly ex- (121), the Hartree-xc kernel in transition space, Eq.

cited configurations. (116), becomes

The Kohn-Sham noninteracting response function χs

(100) has poles at the Kohn–Sham single excitations. 1 X X

Compared with the many-body response function (90), Kiaσ,i′ a′ σ′ = hiki σ|ei(q+G)·r |aka σi

V

χs has fewer poles, since a noninteracting system can- q∈FBZ G,G′

not have double and multiple excitations in linear re- ′ ′

× fHxcσσ′ (q, G, G′ )ha′ ka′ σ ′ |e−i(q+G )·r |i′ ki′ σ ′ i

sponse. Solving the Casida equation in a finite basis and

using the adiabatic approximation for fxc , as is done in × δka −ki +q,G0 δka′ −ki′ +q,G′0 , (122)

19

with the matrix elements defined as This seemingly trivial kernel originates from many-body

Z theory, where one sums up all the ‘bubble’ type dia-

hiki σ|ei(q+G)·r |aka σi ≡ d3 rφ∗iki σ (r)ei(q+G)·r φaka σ (r), grams [18]. Though the form is similar to time-dependent

Hartree, TDDFT RPA is fundamentally different due to

(123) the use of the Kohn-Sham system. The RPA kernel has

where k’s are the Bloch wavevectors of the corresponding seen applications for molecules and is known to produce

wavefunctions, and G0 , G′0 can be any reciprocal lattice reasonably good results. For insulating solids, the RPA

vector. The Kronecker-δs in Eq. (122) are a consequence spectra are missing important features such as excitonic

of Bloch’s theorem. effects (see below).

The Hartree part of fHxc can be shown to be largely The proper way to obtain fxc is via Eq. (97): first

irrelevant for the optical properties of insulators close to approximate the time-dependent xc potential, calculate

the gap [134]; we therefore focus on the xc part in the fxc (r, t, r′ , t′ ) by taking the functional derivative, and

following. For G = G′ = 0 (the so-called head of fxc ) then get the frequency-dependent kernel fxc (r, r′ , ω) via

in the important limit of q → 0, which corresponds to Fourier transform. However, these steps are rarely car-

infinite range in real space, both matrix elements in Eq. ried out in practice, since most of the xc kernels in use are

(122) behave as O(q 1 ). All the local and semilocal xc adiabatic kernels. Recall the adiabatic approximation for

kernels (derived from LDA and GGA in the adiabatic the xc potential, Eq. (69), which uses the ground-state

approximation) have finite values for the head. Since functional and evaluates it at the time-dependent density.

the two matrix elements in Eq. (122) together vanish as The adiabatic approximation for the xc kernel is

O(q 2 ), the head contribution to the sum of Eq. (122)

is zero for all (semi)local kernels. For these kernels, all A

gs

δvxc [n0 ](r) δ 2 Exc [n0 ]

changes to the Kohn-Sham spectrum come from the body fxc (r, r′ ) = = , (125)

δn0 (r′ ) δn0 (r)δn0 (r′ )

of fxc (where G 6= 0, G′ 6= 0).

Gonze et al. [135, 136] pointed out that the head of which is frequency-independent.

fxc has to diverge as q −2 for q → 0 to correctly de- An important example is the ALDA xc kernel:

scribe the polarization of periodic insulators. With the

q −2 divergence, the head of fxc contributes in the sum d2 ehxc (n̄)

ALDA

of Eq. (122), dominating the other parts of fxc [wings fxc (r, r′ ) = δ(r − r′ ) , (126)

dn̄2 n̄=n0 (r)

(G = 0, G′ 6= 0 or vice versa) and body]. Local and

semilocal xc kernels do not have this long-range behavior,

whose exchange part is explicitly given by

and there is no obvious and consistent way of modifying

them to include the long-rangedness. fxALDA (r, r′ ) = −[9πn20 (r)]−1/3 δ(r − r′ ), (127)

The long-range behavior of the xc kernel is unimpor-

tant for low-lying excitations in finite systems such as and the correlation part can be obtained by using Eq.

atoms and molecules, which means that local and semilo- (126) on any of the interpolations of eLDA [19–21].

c

cal xc kernels will work reasonably well. However, for This xc kernel is not only frequency-independent, it is

extended and periodic systems it is crucial to have xc also local. One can derive adiabatic-GGA (AGGA) ker-

kernels with the proper long-range behavior to obtain nels in a similar fashion, starting from any of the standard

correct optical spectra [134, 137]. We will discuss this GGA functionals such as those discussed in Section II E.

further in Section VII D. Adiabatic hybrid kernels, most notably B3LYP, are very

widely used and have contributed much to the success of

TDDFT in quantum chemistry.

VII. APPLICATIONS IN LINEAR RESPONSE

many computer codes in quantum chemistry and mate-

rials science. In this Section we will give an overview of As an example, let us consider the benzene molecule.

some of the most important areas of application. Table III shows eight low-lying singlet and triplet excita-

tion energies of benzene, calculated with various xc func-

tionals [138]. As an overall measure of the accuracy of the

A. Standard approximations for the xc kernel calculations, the mean absolute error (MAE) was also cal-

culated for each functional. Based on this measure, the

To carry out a TDDFT calculation in the linear re- nonhybrid xc functionals (LSD, PBE, and TPSS) per-

sponse formalism, one must know the xc kernel. The form at about the same level, with an MAE of 0.3-0.4

simplest thing to do is to use the random-phase approx- eV. The hybrid functionals (PBE0 and B3LYP) used in

imation (RPA), where the xc kernel is set to zero: this study perform somewhat better, with an MAE rang-

ing from 0.18 to 0.27 eV. As we will see in the following

RPA

fxc (r, r′ , ω) = 0. (124) examples, these findings are quite typical.

20

zene molecule (C6 H6 ) calculated with TDDFT using various

xc functionals with the basis set 6-31++G(3df,3pd), and ge-

ometry optimized using the respective functionals with the

same basis [138]. CASPT2 reference results (Ref), TDHF,

and experimental results from Packer et al. [139]. The mean

average error (MAE) for TDHF excludes the lowest (3 B1u )

triplet transition, which comes out unstable.

3

B1u 4.47 3.98 3.84 3.68 3.84 3.89 — 3.94

3

E1u 4.82 4.61 4.67 4.75 4.72 4.49 4.70 4.76

1

B2u 5.33 5.22 5.32 5.52 5.41 4.84 5.82 4.90

3

B2u 5.05 4.89 4.98 5.12 5.07 5.49 5.57 5.60

1

B1u 6.07 5.94 6.00 6.18 6.05 6.30 5.88 6.20 FIG. 10. Circular dichroism spectrum of D2 -C84 , compar-

ing TDDFT with experiment. (ε: molar decadic absorption

1

E1g 6.12 5.89 5.99 6.38 6.11 6.38 6.54 6.33 coefficient; R: rotatory strength; ∆E: excitation energy). Re-

1

A2u 6.70 6.43 6.50 6.90 6.62 6.86 6.94 6.93 c

produced with permission from ACS from Ref. [144].
2002.

1

E2u 6.71 6.44 6.50 6.95 6.65 6.91 7.11 6.95

xc functional.

MAE 0.30 0.37 0.33 0.18 0.27 0.09 0.26∗

TDHF gives very large errors (over 1 eV), almost al-

ways overestimating the transition energies; any TDDFT

calculation reduces the error by at least a half. Among

the xc functionals, we can distinguish between pure den-

sity functionals (LDA and GGA), meta-GGAs, hybrid

GGAs, and long-range-corrected hybrids (the first eight

functionals in Fig. 9). The LDA and GGAs all give an

MAE of order 0.5 eV. Meta-GGAs (VSXC and TPSS)

give better agreement (about 0.4 eV). But the best

choice are clearly the hybrid GGAs (B3LYP, X3LYP,

B98, mPW1PW91, and PBE0). In this case, the MAE is

reduced to less than 0.25 eV. Similar findings were also

reported in a more recent benchmark study [141].

The long-range-corrected (LC) hybrids such as CAM-

B3LYP give a slightly higher error, owing to a general

overestimation of the transition energies. This is mainly

due to the choice of the test set, in which charge-transfer

excitations are not significantly represented. The advan-

tage of long-range-corrected hybrids emerges for such ex-

Mean Absolute Error (eV) citations in larger molecules.

As these examples illustrate, TDDFT offers an excel-

FIG. 9. Mean absolute error for the lowest vertical excitation lent compromise between computational efficiency and

energies of a test set of 28 medium-sized organic molecules accuracy. TDDFT scales as N 2 to N 3 , depending on the

(103 excited states). Reproduced with permission from ACS implementation; wave-function-based methods of compa-

c

from Ref. [140].
2009. rable accuracy scale at least one or two orders of magni-

tude worse. The current limit of high-end wave-function-

based methods is about 50 atoms [140, 142, 143]. By

Figure 9 shows the MAE for 28 xc functionals and for contrast, TDDFT allows the treatment of molecules con-

HF, obtained by calculating 103 low-lying vertical exci- taining hundreds of atoms. Examples of medium-sized

tation energies for a test set of 28 medium-sized organic systems are shown in Figs. 10 and 11.

molecules [140], compared against accurate theoretical Figure 10 shows the circular dichroism spectrum of a

benchmarks. The Kohn–Sham ground states were ob- large chiral fullerene molecule. TDDFT was able to re-

tained with the same xc functionals that were used, in solve a debate regarding the molecular configuration of

the adiabatic approximation, for the TDDFT calcula- this system [144]. Figure 11 shows the absorption spec-

tions. Identical molecular geometries were used for each trum of an Iridium(III) cyclometallated complex [145].

21

between the electronic and nuclear masses (the proton is

1836 times more massive than the electron), the two sets

of degrees of freedom are essentially decoupled.

The BO Hamiltonian is defined as the full Hamiltonian

(129) minus the nuclear kinetic-energy term:

Ne N

X ∇2rj 1X e

1

ĤBO (r, R) = − +

j=1

2 2 j,k |rj − rk |

j6=k

Nn N

e Xn N

1X Zj Zk X Zk

+ − (130)

.

2 |Rj − Rk | j=1 |rj − Rk |

j,k k=1

j6=k

FIG. 11. Calculated (blue line) and experimental (red line) clear coordinates: this means that the nuclear positions

absorption spectra of a Iridium(III) cyclometallated complex. R1 , . . . , RNn are just treated as a set of given num-

Blue vertical lines correspond to the unbroadened oscillator

bers, indicating a given nuclear configuration; they are

strength of the calculated singlet-singlet transitions. Repro-

c

duced with permission from Elsevier from Ref. [145]. 2009. no longer quantum mechanical operators. For each con-

figuration one solves the Schrödinger equation

C. Potential-energy surfaces

The energy eigenvalues Ej (R) define the landscape of

Consider a system with Ne electrons and Nn nu- potential-energy surfaces, whose dimensionality depends

clei, with nuclear masses Mj and charges Zj , where on the degrees of freedom of the molecule. Thus, for a

j = 1, . . . , Nn . Formally, all electrons and all nuclei diatomic molecule, Ej (R) can be represented simply by a

are quantum mechanical particles, forming an interact- curve as a function of the internuclear distance, whereas

ing Ne + Nn -body system. For instance, the H2 molecule for Nn ≥ 3 it is a function of 3Nn −6 coordinates (3Nn −5

depends on the coordinates of the two electrons, r1 and for linear molecules) and should therefore more appro-

r2 , and on the coordinates of the two protons, R1 and priately be called a “hypersurface”; the potential-energy

R2 : hence, it is a four-body problem. surface is a 2D section through this higher-dimensional

We denote the sets of electronic and nuclear spatial co- space. In common usage, however, the distinction be-

ordinates by r ≡ {r1 , . . . , rNe } and R ≡ {R1 , . . . , RNn }, tween a surface and a hypersurface is usually not made.

respectively. The many-body eigenstates of the system The ground-state potential-energy surface E0 (R) is

are a function of the two sets of coordinates, Ψj (r, R), of particular interest because its minimum defines the

and obey the following many-body Schrödinger equation molecular equilibrium position. However, excited-state

potential-energy surfaces are important too, and play

Ĥ(r, R)Ψi (r, R, t) = Ei Ψi (r, R, t) . (128) a crucial role in chemical reactions, photochemical pro-

cesses, and in spectroscopy.

In the absence of any external potentials, the Hamilto-

All potential-energy surfaces following from Eq. (131)

nian of the coupled electron-nuclear system is given by

are called adiabatic, indicating a complete decoupling of

Ne

X ∇2rj 1X

Ne

1

Nn

X ∇2Rj electronic and nuclear degrees of freedom. The calcu-

Ĥ(r, R) = − + − lation of adiabatic potential-energy surfaces is one of

2 2 j,k |rj − rk | j=1 2Mj

j=1

j6=k

the key tasks of computational chemistry. The low-

Nn N N

est potential-energy surface can be obtained exactly,

e Xn

1 X Zj Zk X Zk in principle, using ground-state DFT; for excited-state

+ −

2 |Rj − Rk | j=1 |rj − Rk | potential-energy surfaces, forces, and vibrational fre-

j,k k=1

j6=k quencies, the appropriate method is TDDFT [144, 146].

≡ T̂e + Ŵee + T̂n + Ŵnn + Ŵen . (129) Figure 12 shows the 1A1 manifold of the CO-stretch

potential-energy curves of planar formaldehyde [147].

As can be seen, Ĥ(r, R) is the sum of an electronic Hamil- These are excited states, several eV above the ground-

tonian containing kinetic energy and electron-electron state potential-energy curve (whose minimum is set at

interaction, T̂e + Ŵee , a similar nuclear Hamiltonian 0 eV). The dashed lines are results from a multirefer-

T̂n + Ŵnn , and an electron-nuclear coupling term Ŵen . ence doubles CI benchmark calculation; the full lines

The full coupled electron-nuclear many-body problem were obtained with TDDFT, using the ALDA with an

is too difficult to solve in general; one usually works in the asymptotic correction. An xc functional with the correct

Born-Oppenheimer (BO) approximation to obtain the asymptotics is important here because these are high-

structure of molecules and solids. The central idea of the lying (Rydberg) excitations.

22

of the intersection point. These difficulties have a lot

to do with the problems of TDDFT to describe double

excitations: an explicitly frequency-dependent xc kernel

fxc (ω) is required for a proper description of conical in-

tersections [148].

in the area of computational (bio)chemistry. However,

applications in solid-state physics and materials science

are emerging at a rapid rate. In this Section we will

highlight some of the most important issues for TDDFT

in solids: the band-gap problem, excitons in insulators,

and plasmons in metals.

characterizes insulating materials. It is defined as follows:

FIG. 12. 1A1 CO-stretch potential-energy curves of planar

formaldehyde (CH2 O). Full lines: TDDFT. Dashed lines:

Eg (N ) = I(N ) − A(N ), (132)

multireference doubles CI. Reproduced with permission from

c

Wiley from [147]. 1998. where I(N ) and A(N ) are the ionization potential and

the electron affinity of the N -electron system, see Eqs.

(24) and (25). Hence, we obtain

A prominent feature in Fig. 12 is the avoided crossing

between the states labeled (π, π ∗ ) and (n, 3py ). TDDFT Eg (N ) = εN +1 (N + 1) − εN (N ) . (133)

reproduces this avoided crossing qualitatively correctly,

thanks to the configuration mixing of individual single- It is important to note that the right-hand side of Eq.

particle transitions induced by the off-diagonal matrix (133) contains the highest occupied Kohn–Sham eigen-

elements Kiaσ,i′ a′ σ′ in the Casida equation (114) [148]. values of two different systems, namely with N and with

The (n, 3py ) curve is almost on top of the exact curve, N + 1 electrons. In a macroscopic solid with 1023 elec-

at least for C–O distances before the avoided crossing. trons, it would of course be impossible to calculate the

On the other hand, the (n, 3dyz ) curve comes out about band gap according to this definition.

1 eV too high, primarily owing to limitations of the xc The band gap in the noninteracting Kohn–Sham sys-

functional used in this calculation. tem, also known as the Kohn–Sham gap, is defined as

There are many TDDFT studies in organic and inor-

ganic photochemistry calculating excited-state potential- Eg,s (N ) = εN +1 (N ) − εN (N ) . (134)

energy surfaces [149–153]. The performance of TDDFT

In contrast with the interacting gap Eg , the Kohn–Sham

depends strongly on the xc functional used (choosing ap-

gap Eg,s is simply the difference between the highest oc-

propriate basis sets is another important factor). Compli-

cupied and lowest unoccupied single-particle levels in the

cations can arise for potential-energy surfaces associated

same N -particle system. This quantity is what is usually

with excitations that have a long-range, charge-transfer

taken as the band gap in standard DFT band-structure

character [154, 155]. In that case, local or semilocal xc

calculations. We can relate the two gaps by

functionals will fail, and one needs to use xc functionals

with the correct long-range behavior, see Section VI C. Eg = Eg,s + ∆xc , (135)

Another source of complications are situations in which

the ground state has an intrinsically multiconfigurational which defines ∆xc as a many-body correction to the

character. This can lead to circumstances in which two Kohn–Sham gap. By making use of the previous rela-

potential-energy surfaces become degenerate and touch tions, we find ∆xc = εN +1 (N + 1) − εN +1 (N ). It turns

each other, which gives rise to so-called conical intersec- out that the many-body gap correction ∆xc can be re-

tions. The name reflects the topology in the vicinity of lated to a very fundamental property of density func-

the point of degeneracy, which looks like an inverted cone tionals, known as derivative discontinuities [158–161].

balancing on the tip of another cone. TDDFT has seri- The so-called band-gap problem of DFT reflects the

ous problems with conical intersections [115, 156, 157]: fact that in practice Eg,s is often a poor approximation

23

E0ex tem (such as photoemission spectroscopy), the optical

' xc gap refers to the lowest neutral excitation. The differ-

H N 1 ence between quasiparticle band gap and optical gap is

the lowest exciton binding energy, E0ex . Excitons can be

Energy

form a Rydberg series, analogous to the hydrogen atom

[116]. The band gap is given by the asymptotic limit of

the excitonic Rydberg series [164] (at least for direct-gap

HN insulators and semiconductors).

TDDFT can be used to calculate optical spectra of ma-

Kohn-Sham gap Band gap Optical gap

(QP gap) terials in principle exactly. In the case of insulators and

semiconductors, this means that it should, in principle,

yield the correct optical gap, the correct excitonic Ry-

FIG. 13. Schematic illustration of the different types of dberg series (if the material under study has one), and

gaps in DFT and TDDFT. The Kohn-Sham gap is defined hence the correct band gap (obtained as the limit of the

as the difference of the highest occupied and lowest unoccu- excitonic Rydberg series). We will discuss in detail in the

pied Kohn-Sham eigenvalues of the N -electron system, see following section how optical spectra of insulators and

Eq. (134). The fundamental band gap [or quasiparticle (QP) semiconductors are calculated with TDDFT in practice.

gap] is the Kohn-Sham gap plus the derivative discontinuity, As always in TDDFT, the burden rests on the xc ker-

see Eq. (135). The optical gap is the band gap minus the nel. In the case of bulk insulators, fxc needs to accom-

lowest exciton binding energy E0ex . The Kohn-Sham gap can

plish two things: it needs to “open up” the gap (i.e., com-

be viewed as an approximation for the optical gap.

pensate the fact that the Kohn-Sham gap underestimates

the band gap), and it needs to produce the electron-hole

interaction that is responsible for the formation of exci-

to Eg , typically underestimating the exact band gap by

tons. Formally, we can write this as follows [165]:

as much as 50%. The reason for this is twofold: com-

monly used approximate xc functionals (such as LDA and qp

fxc = fxc ex

+ fxc . (136)

GGA) tend to underestimate the exact Kohn-Sham gap

Eg,s , and they do not yield any discontinuity correction The xc kernel is written as the sum of a quasiparticle

∆xc . An extreme example for the second failure are Mott part fxcqp

(which opens up the gap) and an excitonic part

insulators, which are typically predicted to be metallic by ex

fxc (which causes excitonic effects). The excitonic part

DFT. This is no accident: in Mott insulators, the exact turns out to be easier to approximate than the quasipar-

Kohn-Sham system is metallic (i.e., Eg,s = 0) so that ticle part (see below). In fact, no suitable approximations

Eg = ∆xc . Clearly, standard xc functionals (where ∆xc qp

to fxc exist at present. To a large extent this is due to

vanishes) are unfit to describe Mott insulators. the fact that the quasiparticle part is intrinsically nona-

It is important to distinguish between the fundamen- diabatic [166]: the frequency-dependence is essential to

tal band gap and the optical gap [124]. The band gap shift the Kohn-Sham gap, and to produce an excitonic

describes the energy that an electron must have so that, Rydberg series [116]. In view of this, one usually ignores

when added to an N -electron system, the result is an the quasiparticle part of fxc and starts from a band struc-

N + 1 electron system in its ground state. The total ture in which the gap has been corrected by other means

charge of the system changes by −1 in this process. By (such as via GW, or with a simple scissor operator [167]).

contrast, the optical gap describes the lowest neutral ex-

citation of an N -electron system: here, the number of

electrons remains unchanged. The two gaps are schemat- 2. Optical spectra of semiconductors and insulators

ically illustrated in Fig. 13 together with the Kohn-Sham

gap. In the optical spectroscopy of solids, a central quantity

The band gap of insulators can be accurately obtained is the complex index of refraction ñ, defined as [168]

from the so-called quasiparticle energies, which are de-

fined as the single-particle energies of a noninteracting ñ2 = ǫmac (ω) , (137)

system whose one-particle Green’s function is the same

as that of the real interacting system (note how this is where ǫmac (ω) is the macroscopic dielectric function. The

different from the definition of the Kohn-Sham system). imaginary part of ǫmac (ω) hence describes the photoab-

In practice, this is often done using the GW method sorption of a solid, as illustrated in Fig. 14 for the

[134, 162, 163]. GW calculations are more demanding case of silicon. To calculate the macroscopic dielectric

than DFT, but they produce band structures of solids function from first principles, we need to take a de-

that agree very well with experiment. Generalized Kohn- tour and first calculate the microscopic dielectric matrix,

Sham schemes [27, 28] can also give good band gaps. ǫ(q, G, G′ , ω), where G and G′ are reciprocal lattice vec-

While the band gap can be measured using techniques tors. The macroscopic dielectric function then follows as

24

provements can be achieved by having a finite head in the

xc kernel. We now list a few xc kernels which have the

proper long-range behavior that is required for a finite

head of the xc matrix.

The long-range corrected (LRC) kernel [136] is a simple

ad-hoc approximation developed mainly for studying the

effect of the long-range behavior. It has the form

LRC α

fxc (q, G, G′ , ω) = − δG,G′ , (141)

|q + G|2

spite its simple form, LRC spectra (with properly chosen

3 4 5 6 α) can be in good agreement with experiments [137, 169]

Z [eV] since the head contribution of the kernel usually over-

whelms the body contributions (sometimes called local

field effects). A simple connection of the parameter α

FIG. 14. Optical absorption spectrum of bulk Si. RPA and with the high-frequency dielectric constant has been sug-

TDLDA fail to reproduce the optical gap and the excitonic gested [137]. This xc kernel should not be confused with

peak. Reproduced with permission from APS from [137]. the long-range correction in ground-state DFT, where it

c

2004. means a correction term to fix the rapid decay of local

and semilocal xc potentials away from nuclei [170].

The Bethe-Salpeter equation (BSE) [134, 171] is a

the limit [134] many-body equation for a two-particle polarization func-

1 tion (which is closely related to the two-particle Green’s

ǫmac (ω) = lim . (138) function) [172]. Today, the BSE, combined with the GW

q→0 ǫ−1 (q, G = 0, G′ = 0, ω)

method, is the most accurate approach to calculating op-

In turn, the inverse dielectric function of a periodic sys- tical properties of materials. However, the scaling of the

tem can be obtained from the response function as computational cost versus system size is not favorable;

the use of GW-BSE has therefore been limited to moder-

ǫ−1 (q, G, G′ , ω) = δGG′ + vG (q)χ(q, G, G′ , ω) , (139) ate system sizes, despite recent progress [173–176]. From

the point of view of TDDFT, the BSE has been an im-

where vG (q) = 4π/|q+G|2 . In TDDFT, the full response portant guide towards the development of very accurate

ex

function is expressed as excitonic xc kernels. The idea is to construct fxc via an

integral equation that features the same four-point re-

′

X X sponse functions that are featured in the BSE [134, 177].

χ(q, G, G , ω) = δG 1 G 2 − χs (q, G1 , G3 , ω) The resulting xc kernel reproduces the results of the full

G′′ G3

−1 BSE [169, 178–184]. However, the computational cost is

essentially as high as that of solving the full BSE; there-

× fHxc (q, G3 , G2 , ω) χs (q, G′′ , G′ , ω), (140) fore, this xc kernel has mainly served as a proof of concept

GG′′

that TDDFT is capable of producing accurate excitonic

where the xc kernel in reciprocal space was defined in Eq. effects. Furthermore, the LRC xc kernel can be shown to

(121). By calculating χ on a frequency grid, one thus emerge from this BSE-based xc kernel in the long-range

obtains the optical spectrum (including a finite broad- limit [185].

ening in order to make the spectrum smooth). The size A computationally much simpler alternative is the re-

of the matrices involved are determined by the number cently proposed ‘bootstrap’ kernel [186, 187], defined as

of k-points associated with the numerical discretization

scheme employed. The spectral contribution from large boot ǫ−1 (q, G, G′ , ω = 0)

fxc (q, G, G′ , ω) = .

G and G′ elements in χ typically decays rapidly, so only χ0 (q, G = 0, G′ = 0, ω = 0)

few reciprocal lattice vectors need to be considered. (142)

As discussed in Section VI E, the head of the xc kernel Since χ0 (q → 0) ∼ q 2 , the bootstrap kernel has the cor-

plays a dominant role in periodic solids. Fig. 14 shows rect O(q −2 ) long-range behavior. The bootstrap kernel

the experimental spectrum of Si together with the calcu- performs well for a wide range of solids, as illustrated in

lated spectrum of ALDA, which has a vanishing head of Fig. 15, and even works for the case of strongly bound

the xc matrix. Besides producing a red-shifted spectrum excitons such as in solid argon or LiF (note that the

due to the band-gap problem, the ALDA spectrum lacks noninteracting response function χ0 typically contains a

the strong excitonic peak near the gap. As expected, lo- band-gap correction such as a scissor operator or GW).

cal and semilocal functionals such as the ALDA break We also briefly mention that the VS98 meta-GGA [188]

25

0 1 2 3 4 5 6 6 9 12 15 18

30 20

(a) c

Ge Diamond

20 15

10

10

5

0

E2

0 v

E1

45 Si 9 AlN

ε2(ω)

30 6

q

15 3

(b)

0 0 k

3 4 5 6 6 9 12 15

30 k q

RPA

GaAs 20 SiC Expt.1

20 Expt.2 k q

10 TDDFT k

10

q

0 0

1 2 3 4 5 6 4 6 8 10 12 14

Energy(eV) Energy(eV)

FIG. 15. Optical absorption spectra of various bulk semi- excitations between valence and conduction band in an in-

conductors calculated with TDDFT using the bootstrap xc sulator, mediated by dynamical xc effects. (b) Particle-hole

kernel, Eq. (142). Reproduced with permission from APS excitations with momentum transfer q across the Fermi sur-

c

from [186]. 2011. face of a simple metal. A plasmon is a coherent superposition

of many such excitations, coupled by Coulomb interactions.

spectra of insulators with TDDFT [189]. yields eigenvalues corresponding to the peaks in the op-

As an alternative to obtaining optical spectra via the tical spectra. Since Eq. (144) avoids the matrix inversion

dielectric matrix, a direct calculation of excitonic binding involved in Eq. (138), the use of f¯H is also a standard

energies of insulators and semiconductors via the Casida practice in the response function approach of TDDFT.

equation is also possible [54, 190–192]. The advantage of

this approach is that excitonic binding energies—which

can be in the meV range for materials such as GaAs—can 3. Metallic systems

be numerically well resolved; this is much more difficult

to do from the dielectric function, which typically yields The optical properties of metallic systems (bulk met-

relatively low-resolution optical spectra such as in Figs. als or metallic nanoparticles) are strongly determined

14 and 15. It is found that the bootstrap kernel yields by the fact that they have a sea of delocalized con-

good results for strongly bound excitons, but is less ac- duction electrons with a Fermi surface. Hence, their

curate for the more weakly bound cases [191]. Accurate low-energy elementary excitation are quite different com-

triplet exciton binding energies are even more difficult to pared to systems with a gap (insulators and semiconduc-

obtain. The development of xc kernels for excitonic ef- tors). Whereas the outstanding features of the optical

fects in solids thus remains an important task for future spectra of insulators are the excitons, metallic systems

research. are dominated by plasmons.

It should be noted that Eqs. (138) and (139) imply Excitons and plasmons are observed using different ex-

that the eigenvalues in the Casida equation approach perimental techniques: excitons are seen in optical ab-

are the poles in ǫ−1 instead of ǫmac , so that the absorp- sorption spectra (i.e., via coupling to transverse optical

tion peaks are not given directly. This problem is solved fields); on the other hand, plasmons couple to longitu-

through a modification of the Hartree kernel: dinal fields, and are thus observed using electron energy

( loss spectroscopy or inelastic light (or X-ray) scattering

¯ ′ 0 G = G′ = 0, spectroscopy [193–196].

fH (q, G, G ) = 4π (143) From a TDDFT perspective, both excitons and plas-

δ ′ otherwise.

|q+G|2 GG

mons are collective excitations of the many-body system.

However, there is a big difference as to what causes the

By using f¯H instead of fH in TDDFT, ǫmac becomes [134]

collective behavior in the Kohn-Sham system. Excitons

can be viewed as a coherent superposition of a large

ǫmac (ω) = lim [1 − vG=0 (q)χ̄(q, G = 0, G′ = 0, ω)] ,

q→0 number of individual particle-hole excitations between

(144) valence and conduction band, mediated via long-range

where χ̄ is the modified response function resulting from dynamical xc effects [116] (see Fig. 16). As we discussed

TDDFT with f¯H . Thus the Casida equation with f¯H in the previous subsection, it is not easy to find xc kernels

26

w EF 12

Exp. present

Exp. Schülke

RPA 25

Energy [eV]

10 TDLDA

TDLDA+LT

Re W

8 20

- Im W Na

6 Al

15

12 Corradini et al.

Hubbard

Gross-Kohn 25

Energy [eV]

q kF 10

8 20

FIG. 17. Schematic illustration of the particle-hole continuum

of a 3D homogeneous electron liquid, and the RPA plasmon

6 Na Al

dispersion. In RPA, the plasmon is undamped until it enters 15

the particle-hole continuum, where it decays into incoherent 0.2 0.3 0.4 0.5 0.6 0.4 0.6 0.8 1

particle-hole excitations (Landau damping). TDDFT gives -1 -1

|Q| [a0 ] |Q| [a0 ]

very similar results [197].

which reproduce excitonic effects: all electron-gas based

comparison of experiment and TDDFT. Reproduced with

approximations (such as ALDA) will fail. c

permission from APS from [196]. 2011.)

On the other hand, plasmon excitations in metallic

systems are relatively easy to capture within TDDFT.

The reason is that plasmons can be viewed as collec-

tive charge-density oscillations, and it is a straightfor- (such as the ALDA) has no imaginary part and hence

ward textbook exercise in electromagnetism to show leaves the plasmon undamped.

that such oscillations arise already from classical elec- Figure 18 shows a comparison of experimental and

trostatic (RPA-type) interactions; many-body xc effects theoretical results for the plasmon dispersions of bulk

only cause relatively minor corrections (but are impor- sodium and aluminum [196]. The agreement is very good

tant and subtle for plasmon damping, see below). One for small plasmon wavevectors, but for larger wavevec-

thus derives the classical plasma frequency as tors all TDDFT approaches fail (even the nonadiabatic

r xc kernel of Gross and Kohn [108]). Good agreement

4πne2 is achieved by a hybrid approach in which many-body

ωpl = . (145) quasiparticle lifetimes are put by hand into the response

m

formalism (TDLDA-LT).

The plasmon dispersion of a homogeneous electron liquid Plasmonic effects are found not only in bulk metals,

can be calculated using TDDFT linear response theory, but also in many types of nanostructures. TDDFT has

along similar lines as finding the zeros of the Lindhard been extensively used for collective excitations in metallic

dielectric function [18]. The analytic form of the plasmon clusters and nanoparticles. In general, the results are

dispersion up to order q 2 is given by excellent: plasmon peaks and line shapes for simple metal

" ! # clusters are very well reproduced, even at the ALDA level

3kF2 1 2 [92, 199]. Applications to gold and silver clusters have

Ω(q) = ωpl 1 + 2 + 8π fxc (q = 0, ωpl ) q ,

10ωpl also been quite successful, and nicely demonstrate the

(146) evolution from atomic-like discrete spectra to plasmon

where the terms without fxc are the RPA result. For spectra as the cluster size increases [200–202].

small q, the plasmon lies outside the particle-hole con- A similar picture holds for doped semiconductor nano-

tinuum, as illustrated in Fig. 17. As soon as the plas- structures such as quantum wells, wires or dots. Here,

mon dispersion enters the particle-hole continuum, it be- collective excitations in the charge and spin channel have

comes subject to Landau damping (decay into incoher- been well studied using TDDFT methods; in general,

ent particle-hole excitations). This damping occurs al- plasmon dispersions are well reproduced [203]. The issue

ready in RPA [198]. But outside the particle-hole con- of plasmon damping in quantum wells has received a good

tinuum, the only source of plasmon damping comes from deal of attention; in particular, intersubband plasmons in

the imaginary part of the xc kernel. The physical ori- quantum wells have been used to test the Vignale-Kohn

gin of the low-q plasmon damping is decay into multiple approximation of TDCDFT [63, 64, 204], with consider-

particle-hole excitations. A frequency-independent fxc able success [205–208].

27

VIII. THE FUTURE OF TDDFT has its clear limitations for situations where a branch-

ing of ionic trajectories occurs, and where the excited

In the final section of our overview, we attempt a fore- states involve multiple pathways. Such phenomena can

cast of the directions in which the field of TDDFT will be described with the so-called surface-hopping schemes

be progressing. We will highlight some areas in which [235–237], in which multiple excited-state potential en-

applications of TDDFT are likely to see a lot of activity ergy surfaces can participate in the dynamics, governed

because of their practical importance. We will also give a by a stochastic hopping algorithm.

list of issues and challenges—some of them formal, some But all of these approaches are based on classical nu-

of them practical—which will keep the TDDFT commu- clear dynamics and are thus missing out on nuclear quan-

nity busy for years to come. tum effects. Important effects of nuclear dynamics such

Biological Systems. It has been said that “if the 20th as interference, decoherence or tunneling are therefore

century was the century of physics, the 21st century will not captured. There are already some efforts underway

be the century of biology” [209]. Without doubt, DFT to develop approaches that combine electronic TDDFT

and TDDFT methods will play a key role in the scien- with nuclear quantum dynamics [238–244]. It can be ex-

tific effort to understand the links between structure and pected that the field will continue to advance towards a

functionality in biochemistry and biology. This is due comprehensive and practical treatment of electronic and

to the fact that DFT is the only method capable of de- nuclear degrees of freedom. This would open up a large

livering ab-initio descriptions of the electronic structure area of interesting new applications of TDDFT.

of systems with tens of thousands of atoms; thanks to Linear and nonlinear optics in materials. In Section

the development of linear-scaling methods, even systems VII D we discussed how linear-response TDDFT is ap-

with millions of atoms are now within reach [210–212]. plied to describe optical properties of materials (insula-

Applications of TDDFT for large biomolecules have tors and metals). It can be expected that this will remain

begun to emerge at a rapid rate [91, 213–219]. Many a highly active area of research. Significant progress can

of these studies are concerned with the electronic and be expected along several directions.

optical properties of DNA fragments, or the properties of There is a need for better xc kernels for solids. It is

light-harvesting complexes. Apart from the availability very likely that these kernels will be expressed in terms of

of the necessary computer power (hardware as well as occupied and unoccupied orbitals, rather than the den-

software), there are several developments in DFT which sity. The bootstrap kernel, Eq. (142), is an important

facilitate this trend towards large organic systems: step in the right direction, but it is not so clear how it

can be systematically improved. For instance, a spin-

• With the range-separated hybrid functionals, we dependent generalization of the bootstrap kernel (which

now have the tools for describing charge-transfer would allow a description of singlet and triplet excitons)

excitations with TDDFT (see Section VI C). is problematic [191].

• A new generation of DFT approaches for van-der- A particularly hot area of research are photovoltaic

Waals interactions has emerged [220–226], which processes in organic systems (polymers or biological light-

allow for first-principles calculations of the struc- harvesting complexes) [245–248]. There is a rich va-

ture of sparse matter, adsorption on surfaces, and riety of photophysical processes involved, such as for-

many other applications. mation and diffusion of excitons, formation of charge-

transfer complexes, relaxation, and charge separation. At

Coupled electron-nuclear dynamics. The coupling of present, no comprehensive ab-initio picture of these pro-

electronic and structural degrees of freedom is a decid- cesses exists. This represents one of the major challenges

ing factor in many functionalities of biological systems. for TDDFT, and should soon be within reach, based on

An example are photoinduced processes such as photoiso- existing methodologies and new developments. A promis-

merization. As discussed in Section VII C, TDDFT gives ing idea is the recently proposed real-time visualization

access to excited-state potential energy surfaces. But of exciton dynamics using the time-dependent transition

things get really interesting when the dynamics goes be- density matrix [81].

yond the Born-Oppenheimer approximation, giving rise In the majority of applications of TDDFT in peri-

to effects such as structural relaxation or ultrafast laser- odic solids, the dielectric function (or related response

driven molecular reorganization or dissociation. In such properties) are calculated, which yield optical spectra or

situations, TDDFT can be combined with molecular dy- scattering cross sections. But there are many nonlinear

namics, at various levels of sophistication [227–229]. For or explicitly time-dependent processes of interest, which

a recent review of nonadiabatic dynamics see Ref. [230]. go beyond response theory and require, in principle, a

The most straightforward TDDFT approach for cou- time-dependent calculation. Real-time TDDFT calcula-

pling electronic and nuclear dynamics is via the Ehren- tions for periodic solids are beginning to emerge [249–252]

fest approximation, which is a mixed quantum-classical to simulate hot carrier generation, dielectric breakdown,

treatment where forces on the classical ions result from a and coherent phonons in semiconductors and insulators.

mean-field average over the electronic states. Ehrenfest Such calculations, in particular if light propagation ef-

dynamics works well in many situations [231–234], but fects are included via a coupling with Maxwell’s equa-

28

tion, pose a significant computational challenge and call tive discontinuity upon change of particle number

for the development of new multiscale or multidomain (briefly mentioned in Section VII D), turns out to

approaches [253, 254]. be crucial for capturing these effects. Most of these

Other developments. Let us conclude with a mixed bag studies are for one-dimensional Hubbard-type lat-

of various formal and practical challenges and unsolved tice systems [273, 274], but three-dimensional sys-

problems for present and future TDDFT research. tems were also considered [275, 276]. In the fu-

ture, work along these lines is likely to make an

• Nonadiabatic xc functionals. Nonadiabatic xc func- impact in the description of realistic strongly cor-

tionals are needed for double excitations in finite related systems and materials, which so far have

systems, for dissipation in extended systems, for ex- remained problematic for (TD)DFT.

citon Rydberg series, for conical intersections, and

many other important phenomena. Electron-gas • Extensions of the formalism. Ground-state DFT

based functionals [63, 64] are of limited use [255]; a has long ago been extended to finite temperatures

connection with many-body approaches seems the [277] and to relativistic systems [14]. The corre-

most promising avenue towards the development of sponding TDDFT versions are not yet available,

simple, practically useful nonadiabatic functionals but would be of great interest for matter under

[129–132]. Another possibility could be via reduced extreme conditions. Finite-temperature TDDFT,

density-matrix-functional theory [256–259]. which might include elements of nonequilibrium

thermodynamics and time-dependent thermal en-

• Open systems. TDDFT for open systems is of inter- sembles, could also be of interest for thermal trans-

est for the description of transport through nano- port and thermoelectric properties. Relativistic

or mesoscopic systems, where a region of interest TDDFT has been used for calculating molecular ex-

(e.g, a molecule) is connected to energy and parti- citation energies and response properties [278–282],

cle reservoirs via metallic leads [260]. It is also of and real-time Dirac-Kohn-Sham calculations have

interest for treating dissipative dynamics. The cou- been explored [283], but formally rigorous general

pling to a reservoir can be formally treated within existence proofs have yet to be worked out. Some

TDDFT in various ways: with a master equation promising developments have recently occurred in

approach [261], using stochastic methods [262–264], the application of TDDFT methods for quantum

and by mapping the open physical system onto a electrodynamics [284, 285].

noninteracting closed system [265–267]. The formal

aspects are complicated and subject of ongoing de-

bate [268]; practical xc functionals for open systems ACKNOWLEDGMENTS

and applications beyond simple model systems can

be expected in the future.

This paper is based in part on a two-weeks course on

• Strongly correlated systems. There has been some excitations in materials, delivered in July 2012 at the

interesting recent work in which TDDFT meth- Universidade Federal do ABC at Santo André, sponsored

ods were successfully applied to the transport in by the American Physical Society and the Sociedade

strongly correlated model lattice systems exhibit- Brasileira de Fı́sica. We also acknowledge support from

ing Coulomb blockade and the Kondo effect [269– NSF Grant No. DMR-1005651. We thank Yonghui Li

272]. A subtle feature of the xc potential, its deriva- for preparing Figures 7 and 8.

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