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A brief compendium of time-dependent density-functional theory

Carsten A. Ullrich and Zeng-hui Yang


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

I. PREFACE II. GROUND-STATE DFT IN A NUTSHELL

This paper presents an introduction to and a survey A. The many-body problem


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

Here, Ô is a Hermitian operator corresponding to a quan- n0 ( x )


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

Meaning of the wave function. The Kohn-Sham system where


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

approximation (LDA), gives very useful results in many


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

approximation such as the LDA or GGA. The main


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 .

the time-dependent density and current density, n(r, t)


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

The first to deliver an existence proof for TDDFT were é Ñ2 ù ¶


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 ¢)

v(r, t) − v ′ (r, t) 6= c(t) (49) Time


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

This section can be skipped by readers who may be System 1: w(r r )


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

An important question in ground-state DFT is the fol-


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

considered pathological and thus are not considered to 1 t=0


t=0.1
pose any threat. However, it turns out [53, 54] that the t=0.2

time-dependent density n(x,t)


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

scription, the nuclei and electrons interact through the


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

time-Taylor-expansion density n(x,t)


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

in Fig. 6 (the t-TE density is defined as the result of


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)

However, this map is determined up to within a gauge


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

Dipole moment (a.u.)

Time (a.u.)
Intensity (a.u.)

Energy (eV)

FIG. 7. Time-dependent Kohn-Sham calculation for a CO2


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.

be numerically implemented in various ways [84]; an ex-


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]:

χ(r, t, r′ , t′ ) = −iθ(t − t′ )hΨgs |[n̂(r, t − t′ ), n̂(r′ )]|Ψgs i .


Z Z

(88) n1 (r, t) = dt d3 r′ χs (r, t, r′ , t′ )v1s (r′ , t′ ) . (95)
16

Here, χs (r, r′ , t − t′ ) is the density-density response func- is then given by


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

TDDFT is very similar to describing the small oscilla-


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)

tiple) excitations, i.e., the associated many-body excited


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

Linear-response TDDFT has been implemented in B. Molecular excitations


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

TABLE III. Low-lying excitation energies (in eV) of the ben-


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.

LDA PBE TPSS PBE0 B3LYP Ref TDHF Exp

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

BO approximation is that because of the large difference


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

This Hamiltonian depends parametrically on the nu-


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

ĤBO (r, R)Ψj (r, R) = Ej (R)Ψj (r, R) . (131)


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

it typically produces the wrong topology in the vicinity


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].

D. Optical properties of solids

At present, the majority of applications of TDDFT are


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.

1. The band gap versus the optical gap

The fundamental band gap Eg is a key quantity that


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

in which electrons are added or removed from the sys-


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

viewed as bound electron-hole pairs, whose bound states


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

down for the highly non-local excitonic effects. Big im-


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

where α is a system-dependent fitting parameter. De-


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. 16. (a) Excitons arise from a coupling of single-particle


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.

has recently shown some promise for calculating optical


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].

FIG. 18. Plasmon dispersions of bulk sodium and aluminum:


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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