Density Functional Theory

In density functional theory (DFT) the energy of a system is given as a sum of six

components:

EDFT = ENN + ET + Ev + Ecoul + Eexch + Ecorr

The definitions for the nuclear-nuclear repulsion ENN, the nuclear-electron

attraction Ev, and the classical electron-electron Coulomb repulsion Ecoul energies
are the same as those used in Hartree-Fock theory. The kinetic energy of the
electrons ET as well as the non-classical electron-electron exchange energies
Eexch are, however, different from those used in Hartree-Fock theory. The last term
Ecorr describes the correlated movement of electrons of different spin and is not
accounted for in Hartree-Fock theory. Due to these differences, the exchange
energies calculated exactly in Hartree-Fock theory cannot be used in density
functional theory.

Various approaches exist to calculate the exchange and correlation energy terms in
DFT methods. These approaches differ in using either only the electron density
(local methods) or the electron density as well as its gradients (gradient corrected
methods or generalized gradient approximation, GGA). Aside from these "pure"
DFT methods, another group of hybrid functionals exists, in which mixtures of
DFT and Hartree-Fock exchange energies are used.

1) Local methods
The only local exchange functional available in Gaussian is the Slater functional.
Combination with the local VWN correlation functional by Vosko, Wilk and
Nusair gives the Local Density Approximation (LDA) method. For open shell
systems, using unrestricted wavefunctions, this is also referred to as the Local Spin
Density Approximation (LSDA). This method is used in Gaussian with either
the LSDA or SVWN keyword. A sample input for the frequency calculation for the
methanol-1-yl radical using the SVWN functional and the 6-31G(d) basis set is as
follows:
#SVWN/6-31G(d) freq            
SVWN/6-31G(d) freq methanol-1-yl radical

0 2
C1
O2 1 r2
H3 2 r3 1 a3
H4 1 r4 2 a4 3 d4
H5 1 r5 2 a5 4 d5

r2=1.35454381
r3=0.97675734
r4=1.09713107
r5=1.09208721
a3=108.95266528
a4=119.30335589
a5=113.0329959
d4=-26.58949552
d5=-149.77421707

Please observe that the acrynom VWN is used to indicate different functionals in

different software packages. While in Gaussian this keyword refers to functional
III described in the VWN-paper (S. J. Vosko, L. Wilk, M. Nusair, Can. J.
Phys. 1980, 58, 1200), most other packages refer to functional V in the same paper.
This latter functional can also be used in Gaussian with the VWN5 keyword.

2) Gradient corrected methods

The gradient-corrected exchange functionals available in Gaussian include (given
with their abbreviations in parenthesis):

 Becke88 (B)
 Perdew-Wang (PW91)
 Modified Perdew-Wang by Barone and Adamo (MPW)
 Gill96 (G96)
 Perdew-Burke-Ernzerhof (PBE)

and the gradient-corrected correlation functionals are

 LYP by Lee, Yang, and Parr (LYP)

 Perdew-Wang (PW91)
 Perdew 86 (P86)
 Becke96 (B96)
 Perdew-Burke-Ernzerhof (PBE)

In all cases, the names of these functionals refer to their respective authors and the
year of publication. All combinations of exchange and correlation functionals are
possible, the keywords being composed of the acronyms for the two functionals.
The frequently used BLYP method, for example, combines Becke's 1988 exchange
functional with the correlation functional by Lee, Yang, and Parr. An input file for
the BLYP frequency calculation of the methanol-1-yl radical is:
#P BLYP/6-31G(d) freq

BLYP/6-31G(d) opt min methanol radical

0 2
C1
O2 1 r2
H3 2 r3 1 a3
H4 1 r4 2 a4 3 d4
H5 1 r5 2 a5 4 d5
           
r2=1.38575119
r3=0.98034945
r4=1.09658704
r5=1.09123991
a3=108.13230593
a4=118.45265645
a5=112.14316572
d4=-29.40173022
d5=-145.83450795

Another frequently used GGA functional is BP86 composed of the Becke 1988

exchange functional and the Perdew 86 correlation functional.
The PW91 functional combines exchange and correlation functionals developed by
the same authors in 1991. The keywords used in Gaussian for a particular GGA
functional are combinations of the acronyms for exchange and correlation
functionals. Use of the PW91 exchange and correlation functionals thus requires
the keyword PW91PW91.

3) Hybrid functionals
The basic idea behind the hybrid functionals is to mix exchange energies calculated
in an exact (Hartree-Fock-like) manner with those obtained from DFT methods in
order to improve performance. Frequently used methods are:

 Becke-Half-and-Half-LYP (BHandHLYP) uses a 1:1 mixture of DFT and

exact exchange energies:
EXC = 0.5*EX(HF) + 0.5*EX(B88) + EC(LYP)

 Becke-3-LYP (B3LYP) uses a different mixing scheme involving three

mixing parameters:
EXC = 0.2*EX(HF) + 0.8*EX(LSDA) + 0.72*DEX(B88) + 0.81*EC(LYP) +
0.19*EC(VWN)
In this latter case, the B88 gradient correction to the local LSDA exchange
energies carries its own scaling factor of 0.72. The three scaling factors have
been derived through fitting the parameters to a set of thermochemical data
(G1 set).
  PBE0 uses a 1:3 mixture of DFT and exact exchange energies:
EXC = 0.25*EX(HF) + 0.75*EX(PBE) + EC(mPW91)

 B98 (Becke98) is based on a 10-parameter equation scaling components of

exact exchange, GGA exchange and GGA correlation. All parameters have
been optimized simultaneously to fit thermochemica data collected in the
extended G2 data set:
EXC = 0.2198*EX(HF) + EX + EC

The Becke-half-and-half-LYP method is used with the BHandHLYP keyword, the

very popular Becke-3-LYP method is used with the B3LYP keyword, and the
PBE0 method with the PBE1PBE keyword. A sample input file for the B3LYP
frequency calculation on the methanol-1-yl radical is:
#P B3LYP/6-31G(d) freq

Becke-3-LYP/6-31G(d) opt min methanol radical

0 2
C1
O2 1 r2
H3 2 r3 1 a3
H4 1 r4 2 a4 3 d4
H5 1 r5 2 a5 4 d5
           
r2=1.37007444
r3=0.96903862
r4=1.08886325
r5=1.08381987
a3=108.87657926
a4=118.49962766
a5=112.61039767
d4=-29.19863769
d5=-146.73450089

It is important to note that implementations of the B3LYP and BHLYP functionals

in different programs (Gaussian, Turbomole, Jaguar, Q-Chem) vary somewhat.
Other hybrid functionals available in Gaussian are: B3P86 uses the P86 correlation
functional instead of LYP, but retains the three parameters derived for
B3LYP; B3PW91 uses the PW91 correlation functional instead of LYP, but retains
the three parameters derived for B3LYP; B1B96, a one parameter functional
developed by Becke using the Becke 96 correlation
functional; MPW1PW91 developed by Barone and Adamo using a modified
version of the PW91 exchange functional in combination with the original PW91
correlation functional and a mixing ratio of exact and DFT exchange of 0.25 : 0.75.

4) User-defined models
Calculation of reaction and activation energies in either radical reactions or
transition metal mediated reactions often shows that the mixing ratio of HF- and
DFT-exchange is not optimal for a given purpose. The definition of user-defined
models tailored to a certain purpose is therefore sometimes necessary. This can be
achieved by first choosing gradient corrected exchange and correlation functionals
from the list of available choices and then specifying the mixing ratios of the
various exchange and correlation energy terms. For this latter step Gaussian uses
the general formula:

EXC = P2EXHF + P1(P4EXSlater + P3dEXnon-local) + P6EClocal + P5dECnon-local

The values for the parameters P1 - P6 are provided through the IOP switches
IOP(5/45=xxxxyyyy), IOP(5/46=xxxxyyyy), and IOP(5/47=xxxxyyyy) with P1 =
xxxx/1000 from IOP(5/45) etc. The use of this facility will be illustrated with
the MPW1K functional by Truhlar and coworkers (B. J. Lynch, P. L. Fast, M.
Harris, D. G. Truhlar, J. Phys. Chem. A 2000, 104, 4811) developed to optimize
reaction and activation energies of free radical reactions. This method is very
similar to the MPW1PW91 hybrid functional, but uses a mixing ratio of exact and
DFT exchange energy terms of 0.428 : 0.572. An input file for the methanol-1-yl
radical frequency calculation at the MPW1K/6-31G(d) level is:
#P MPWPW91/6-31G(d) freq
IOP(5/45=10000428) IOP(5/46=05720572)
IOP(5/47=10001000)

MPW1K/6-31G(d) opt min methanol radical

0 2
C1
O2 1 r2
H3 2 r3 1 a3
H4 1 r4 2 a4 3 d4
H5 1 r5 2 a5 4 d5            
r2=1.35355619
r3=0.95690342
r4=1.08170148
r5=1.07685321
a3=109.38001654
a4=118.56662303
a5=112.99211737
d4=-29.64928765
d5=-147.42512309

The gradient corrected MPWPW91 functional is chosen here as the basis of the

hybrid method and the amount of exact exchange is specified through parameter
P2. The composition of the functional is also described in the output file in a
compact format:

IExCor= 908 DFT=T Ex=mPW+HF Corr=PW91 ScaHFX= 0.4280

 ScaDFX= 0.5720 0.5720 1.0000 1.0000

The value given after ScaHFX corresponds to P2 while the four values listed

after ScaDFX are P3 - P6. Please observe that theses lines are only printed when
using the extended output option of Gaussian. Before using this facility with a
particular version of Gaussian, please make sure that your IOP-directives are read
correctly. In some versions of Gaussian, the options P1 - P6 are set with IOP(3/76) -
IOP(3/78) instead of IOP(5/45) - IOP(5/47). In this latter case, the values of P1 -
P6 are given in five-digit format. The keyword line for the PBE0 frequency
calculation thus becomes:

#P PBEPBE/6-31G(d) freq
IOP(3/76=1000002500) IOP(3/77=0750007500) IOP(3/78=1000010000)

Absolute and relative CPU-times for DFT- and Hartree-Fock-calculations depend

dramatically on the size of the system under investigation, the computer hardware
and the operating system used. The following table contains CPU times (in
seconds) for all frequency calculations on the methanol-1-yl radical described
above with Gaussian 03, Rev. B.03. The platforms used are the CIP-room Pentium
4/2 GHz computers under LINUX. In all cases the frequency calculation has been
performed on the structure optimized at the given theoretical level. The 6-31G(d)
basis set has been used in all cases.

 CPU (P4/2GHz)   vib(1)   vib(2)   vib(3) 

 method 
[sec] [cm-1] [cm-1] [cm-1]
USVWN/6-31G(d) 31 3690 1455 1036
UBLYP/6-31G(d) 69 3599 1463 1042
UB3LYP/6-31G(d) 71 3761 1508 1072
 UMPW1K/6-31G(d)  73 3950 1552 1102
UHF/6-31G(d) 11 4123 1627 1156
 obsvd.  - 3650 1459 1056

Despite all platform-dependend variations, it is clear that hybrid DFT calculations

are similarly laborious as GGA calculations, while local DFT methods are
somewhat and HF-calculations much cheaper. In matching calculated (harmonic)
gas phase vibrational frequencies with experimentally observed anharmonic values
measured in a matrix (R. D. Johnson III, J. W. Hudjens, J. Phys. Chem., 1996, 100,
19874), please remember that uniform scaling is often performed to improve
correspondence (see our earlier discussion of this point). The values reported here
are unscaled. A general trend visible in this example is the increase of vibrational
frequency wavenumbers with an increase in the amount of Hartree-Fock exchange
contributions (varying between 0 and 100% from the second entry to the bottom in
Table 1).

5) Further technical considerations

Evaluation of the exchange-correlation energies of all density functional methods
implemented in Gaussian involves a grid-based numerical integration step. The
computational effort required for this step strongly depends on the selected grid
size. The larger the number of integration points per atom, the higher is the
computational cost and the better the numerical accuracy of the calculation.
Several predefined grids are available in Gaussian, which can be used through the
keyword

int=(gridsize) or int=(Grid=gridsize)

Alternatively, the grid size can also be specified with IOP settings, using
either IOP(5/44=gridsize) or IOP(3/75=gridsize), depending on the version
of Gaussian. The following are acceptable values for gridsize:

 (radial shells *
 corresponding   CPU frequencies
gridsize angular Etot
IOP setting [sec]  (cm-1)
points)
 -110.9325 -0.0015
(35*110),
 CoarseGrid 2 33.8  -115.0520127  -0.0009 -0.0008
pruned
24.6825 59.6546
 -30.5802 0.0015
(50*194),
SG1Grid 1 45.1  -115.0520371  0.0015 0.0016
pruned
10.5877 29.2740
 -20.7294 -8.3913
(75*302),  
finegrid 4 77.1 0.0009 0.0009 0.0014
pruned -115.0520326 
11.1426
 -0.0013 -0.0013
(99*590),
ultrafine 5 192.7  -115.0520324  0.0011 2.6708 4.0642
pruned
14.0308
(mmm*nnn),
mmm,nnn mmmnnn - - -
not pruned

The CPU times and total energies listed here (in sec.) together with the grid
specifications are those for the UB3LYP/6-31G(d) frequency calculation on the
methanol radical mentioned before on the CIP room Pentium 4 LINUX PCs. It is
clear from these results that neither the total electronic energy nor the low-
frequency vibrations converge quickly with increasing grid size. Thus, for each
application it must be decided, whether the substantial computational effort for a
very high grid size is justified. It is also important to note that the energy variation
with grid size is significant enough that all calculations for stationary points on the
same potential energy surface must be performed with the same grid in order to be
comparable!

In addition to the grid selection for integral evaluation using

the int=(gridsize) keyword, a particular grid can also be selected for the calculation
of second derivatives using the CPHF=gridsize keyword. The available options
for gridsize are identical in both cases. If no explicit grid is specified through
the CPHF keyword, the following relations exist between the grids used for
integral and second derivative calculations:

gridsize used for grid used for

 integral evaluation  second derivatives
CoarseGrid CoarseGrid
SG1Grid CoarseGrid
finegrid CoarseGrid
ultrafine SG1Grid
(mmm*nnn) (mmm*nnn)

These combinations are usually appropriate for most systems. The default grid size
for integral evaluation in the most recent versions of Gaussian is finegrid. Better
grids are required for kinetic isotope effect calculations, the optimization of
stationary points on very flat potential energy surfaces, and IRC-following on flat
potential energy surfaces. Increasing the CPHF grid size over what is specified per
default through the integral grid selection is rarely helpful. Smaller grids can be
quite useful to speed up geometry optimizations of large systems, especially when
still far away from the next stationary point.

6) Treating open shell systems

For practical reasons the DFT methods also use a DFT "wavefunction" constructed
as an antisymmetrized product of one electron functions (now termed Kohn-Sham
orbitals). As in Hartree-Fock theory, electrons of unlike spin can either use the
same spatial orbitals (restricted DFT methods) or different spatial orbitals
(unrestricted DFT methods). Specification of a restricted open shell wavefunction
for the Becke3LYP hybrid functional requires the ROB3LYP keyword, while the
unrestricted version is specified using UB3LYP. If no explicit choice is made in
the input file, open shell systems are treated with the unrestricted approach by
default. It should be noted that unrestricted DFT methods (GGA or hybrid
functionals alike) are much less affected by the phenomenon of spin contamination
than Hartree-Fock theory and also give much better predictions of ESR spectra of
organic radicals. The UB3LYP/6-31G(d) calculation of the allyl radical is achieved
with the following input file:
#UBecke3LYP/6-31G(d) scf=(tight)

UB3LYP/6-31G(d) ally radical (C2v)

0 2
H
C,1,r2
C,2,r3,1,a3
C,2,r3,1,a3,3,180.
H,3,r5,2,a5,1,0.
H,4,r5,2,a5,1,0.
H,3,r7,2,a7,1,180.            
H,4,r7,2,a7,1,180.

r2=1.09054601
r3=1.38611149
r5=1.08492921
r7=1.08690606
a3=117.45043254
a5=121.64506508
a7=121.12827199

Comparison of the expectation value of the <S2> operator calculated at the UHF/6-
31G(d) level (0.9729) with that obtained at UB3LYP/6-31G(d) (0.7818) shows that
the spin contamination problem is much reduced with DFT methods. From the
construction principle of the hybrid DFT methods it is clear that a larger HF-
exchange component will also give rise to larger amounts of spin contamination.
Using the allyl radical at the UB3LYP/6-31G(d) structure as an example, the <S2>
value amounts to 0.7650 at the BLYP/6-31G(d) level and to 0.8228 at the
BHandHLYP/6-31G(d) level. The precise values of the expectation value of the
<S2> operator will also depend to some extend on the basis set used.

Another important point to consider in DFT calculations concerns the self

interaction error resulting from an artificial interaction of the electron density with
itself. While the definition of the exchange and Coulomb energies in Hartree-Fock
theory leads to a perfect cancellation of these self interaction terms, the
cancellation is incomplete in DFT methods. As nicely explained by Koch and
Holthausen in their monograph on DFT methods, this can be easily demonstrated
using the hydrogen atom. The exact energy for this one-electron system is
-0.50000 Hartree. As there is no second electron in the system, no correlation
energies have to be calculated and Hartree-Fock theory is able to provide the exact
answer in the complete basis set limit. Using a basis set considered "large" for
molecular systems such as the cc-pVQZ basis set, a value of -0.499946 Hartree is
indeed obtained. Due to the parameterized exchange and correlation functionals,
however, much more negative values can be obtained in particular with hybrid
DFT functionals. Using the same basis set, the UB3LYP functional predicts a
value of -0.502346 Hartree!!
last changes: 12.12.2006, HZ
questions & comments to: zipse@cup.uni-muenchen.de