Chemistry Reference
In-Depth Information
CHAPTER 3
Excited States from Time-Dependent
Density Functional Theory
Peter Elliott,
a
Filipp Furche,
b,c
and Kieron Burke
c
a
Department of Physics and Astronomy, University of California,
Irvine, California
b
Institut f ¨ r Physikalische Chemie, Universit ¨ t Karlsruhe,
Karlsruhe, Germany
c
Department of Chemistry, University of California, Irvine,
California
INTRODUCTION
Ground-state density functional theory
1-3
has become the method
of choice for calculating ground-state properties of large molecules because
it replaces the interacting many-electron problem with an effective single-
particle problem that can be solved much more quickly. It is based on rigorous
theorems
1,2,4
and a hierarchy of increasingly accurate approximations, such
as the local density approximation (LDA), generalized gradient approxima-
tions (GGAs),
5-7
and hybrids of exact exchange with GGA.
8
For example, a
recent ground-state calculation
9
for crambin (C
203
H
317
N
55
O
64
S
6
), a small
protein, using TURBOMOLE
10
on a 1.5-GHz HP Itanium workstation took
less than 7 h, which is extraordinarily fast for 2528 electrons, with 5587 con-
tracted Cartesian Gaussian basis functions. Formally, however, ground-state
