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Density functional theory is now the method of choice for calculating the electronic structure of
complex systems, and time-dependent density functional theory (TDDFT) is now the preferred
method for calculating spectroscopic properties of large molecules. The validity of the theory
depends mainly on the quality of the approximation to the unknown exchangecorrelation
energy. In the present paper we consider TDDFT calculations of electronic excitation energies
and oscillator strengths. We show that the M06-2X and M08-HX density functionals perform as
well as and better than the range-separated CAM-B3LYP functional for charge transfer
excitations with intermediate spatial overlap but have better performance for bond energies,
noncovalent interactions, and chemical reaction barrier heights for representative systems; we
conclude that M06-2X and M08-HX should be preferred for studies requiring the exploration of
potential energy surfaces as well as electronic excitation energies, provided that those excitations
with the longest-range charge transfer are excluded.
Electronic excitations of molecules may be classied in of shortcomings.11,12 For example, many common DFAs give
terms of three ideal cases: local valence excitations in which inaccurate results for Rydberg states. The M06-2X
the principal quantum number does not change (e.g., functional13 gives accurate results for local valence excitations
2sp2 nO ! 2pp CO in acetone),1 high Rydberg transitions and for low Rydberg states, but not for the more challenging
(e.g., excitation of states with principal quantum number problem of spatially nonoverlapping charge transfer excita-
4 10),2 and charge transfer excitations between charge dis- tions.13 The M06-HF functional14 is accurate for spatially
tributions in dierent regions of space (e.g., a charge shift nonoverlapping charge transfer but less accurate than M06-2X
between neighboring peptide units in dipeptides).3 However, for local valence and low Rydberg states,13 and it signicantly
real excited states are often not purely one of these ideal types. overestimates the transition energies for p - p* states.15
In particular, low Rydberg states often have mixed valence A recent study15 concluded that No functional. . .shows
Rydberg character,4,5 and many charge transfer excitations are acceptable accuracy for all three of valence, Rydberg, and
between orbitals with appreciable spatial overlap (the spatial charge transfer excitations.
overlap of an excitation from orbital c1 to orbital c2 refers to Peach et al.6 recently presented a diagnostic called L that
the overlap of the moduli of the orbitals, |c1||c2|, rather than quanties the degree of spatial overlap in charge transfer
the usual orbital overlap integral, hc2|c1i).6 A challenge for excitations, with L = 0 corresponding to no spatial overlap
quantum chemistry is to develop accurate methods to calculate and L D 1 corresponding to a local valence excitation. They
electronic excitation energies for both pure and mixed types of found that the CAM-B3LYP density functional16 performs
transitions, even for large molecules. well even for L D 0. In a subsequent study17 of the protonated
Time-dependent density functional theory is a very Schi base 11-Z-cis-retinal (1) and the analogous 11-Z-cis-7,8-
appealing choice for such calculations because it includes dihydroretinal (2), following upon previous work,18 they
dynamical correlation energy and is much more aordable found that the CAM-B3LYP functional performs well for
than post-HartreeFock wave function methods.710 In ve excitation energies with L in the range 0.230.72,
practice, TDDFT calculations in chemistry are almost always whereas the popular B3LYP functional19 performed well for
carried out in the adiabatic approximation, using frequency- L = 0.500.72 but has large errors for L = 0.230.30.
independent density functional approximations (DFAs) One may classify DFAs in various ways, and for the present
developed for the ground state. Such calculations, although discussion we distinguish three classes: local DFAs, global
they have been very useful, are known to suer from a number hybrids (including doubly hybrids), and range-separated
hybrids. Local DFAs depend on the local spin-up and spin-
down electron densities (here called the spin densities), and
a
Department of Chemistry, Nankai University, Tianjin, 300071, possibly on their local gradients or higher derivatives, and/or
P. R. China. E-mail: lrf@nankai.edu.cn
b
Department of Chemistry and Supercomputing Institute, on the local spin kinetic energies (calculated from the local
University of Minnesota, 207 Pleasant Street S.E., Minneapolis, values of the spin-orbitals, which are themselves functionals of
Minnesota 55455-0431, USA. E-mail: zheng@comp.chem.umn.edu, the spin densities). Examples include BP8620,21 and M06-L.22
truhlar@umn.edu Local hybrid DFAs include a xed percentage of nonlocal
w Electronic supplementary information (ESI) available: Geometries
of the molecules and additional details of the database comparisons. HartreeFock (HF) exchange23 or xed percentages of HF
See DOI: 10.1039/c0cp00549e exchange and of nonlocal correlation functionals that depend
This journal is c the Owner Societies 2010 Phys. Chem. Chem. Phys., 2010, 12, 1269712701 12697
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12698 Phys. Chem. Chem. Phys., 2010, 12, 1269712701 This journal is c the Owner Societies 2010
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The next four functionals in Tables 1 and 2 have 20 r X r 54. performance is poor, consistent with our previous assessment.15
We see excellent accuracy for both M06-2X and M08-HX with This is unfortunate because M06-HF has been shown to be very
poorer accuracy for B3LYP and M06, neither of which is accurate for long-range charge transfer transitions,13 where
accurate for L r 0.30. Since the M06-2X and M08-HX most local DFAs and global hybrids fail abysmally. A key
functionals perform well, it is useful to briey indicate how these conclusion here is that it is not sucient to have high
functionals were determined. By the time that M06-HF and HartreeFock exchange at large interelectronic separations in
M06-2X were designed, Zhao and one of the authors, building order to predict accurate results for charge transfer excitations.
on previous work by others,23,3036 had developed considerable This point has also been made previously.13
experience about what kind of functional form and parametri- The next three functionals in the tables have X = 100 for
zation scheme is required for a density functional approximation large interelectronic separations and X = 0 for small inter-
Published on 24 August 2010. Downloaded by FAC DE QUIMICA on 02/03/2016 21:38:11.
to be broadly accurate,14,22,3739 and that experience was used to electronic separations. Unfortunately the simple expedient of
design new functional forms depending on spin-up and spin- only removing long-range self-interaction by range separation
down kinetic energy densities and HartreeFock exchange as does not give accurate results and cannot be recommended.
well as the spin-up and spin-down electron densities and their CAM-B3LYP and oB97X-D represent a more sophisticated
reduced gradients. Because these functionals have high percen- strategy in which X Z 65 at large interelectronic distance, and
tages of HartreeFock exchange (52.23% for M08-HX and 54% 19 r X r 22.2036 at small interelectronic separation. The
for M06-2X) they are not designed for treating transition metal tables show that CAM-B3LYP performs excellently, with a
chemistry, and so they were parametrized against data for mean error in excitation energies only a factor of 1.8 larger
main-group chemistry, in particular against atomization energies, than M08-HX and 63% larger than M06-2X, and with a
bond energies, proton anities, ionization potentials, electron mean error in oscillator strengths 1924% lower than those
anities, barrier heights, atomic energies, isomerization energies methods. The oB97X-D method is not quite as accurate as
of p systems, and noncovalent interaction energiesall for the three best methods, but is comparable to M06, which has
ground electronic states.13,24 X = 27 at all interelectronic separations.
M06-HF is the only functional in the tables with X = 100 for The most striking conclusion of this study is that, even
the entire range of internuclear separations. Unfortunately the though they do not have X = 100 at long range and do not
employ range separation, M06-2X and M08-HX perform well
Table 3 Mean signed errors and mean unsigned errors (kcal mol1 even for a transition with L as low as 0.23; thus these
per bond) in two bond energy databases functionals can be recommended for all but the longest-
range charge transfer excitations. This is important because
AE6a ABDE4b
MGBE10 these functionals have very broad accuracy for ground-state
MSE MUE MSE MUE MUE properties.13,24,40 To illustrate this broad accuracy, Tables 35
M06-2X 0.17 0.27 0.29 0.75 0.46 give additional results for the three DFAs that perform best in
M08-HX 0.31 0.57 0.46 0.62 0.59 Tables 1 and 2. These additional results are single-point energy
CAM-B3LYP 0.10 0.36 5.44 5.44 2.39 calculations on standard databases. The sources of the geo-
a
Basis set is MG3S; geometries are from ref. 42 and are given in the metries used for these databases are specied elsewhere,4145
ESIw; accurate values of the atomization energies are from ref. 41; spin- and the AE6 geometries are given in ESI.w
orbit contributions were added to the density functional calculations as Table 3 gives the mean signed and unsigned errors for
described in ref. 46. b Basis set is 6-311+G(3df,2p); geometries are from
two bond energy databases, AE641,42,46 and ABDE4.22,39,43
ref. 43; the accurate bond energies are tabulated in ref. 22.
AE6 contains six molecules with representative atomization
Table 4 Mean unsigned errors (kcal mol1) for noncovalent binding energiesa
Table 5 Mean signed errors and mean unsigned errors (kcal mol1) in 24 barrier heights of the DBH24/08 databasea
This journal is c the Owner Societies 2010 Phys. Chem. Chem. Phys., 2010, 12, 1269712701 12699
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energies, namely SiH4, SiO, S2, propyne, glyoxal, and cyclo- Air Force Oce of Scientic Research by grant no. FA9550-
butane, and, as in previous work,13,41 the results are divided by 08-1-0183 and by the National Science Foundation by grant
the average number of bonds per molecule to put them on a nos. CHE07-04974 and CHE09-56776.
per-bond basis. ABDE4 contains the following four bond
energies: methylmethyl, methylmethoxy, methylisopropyl,
and isopropylmethoxy. To make the overall conclusion more
clear we also combine the errors of AE6 and ABDE4 into a References
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