Essentials of Computational Chemistry

284 8 DENSITY FUNCTIONAL THEORY
Table 8.1 (continued)
Level of theory Test sets a
A B C D E
B97/numeric 1.8
(5.5)
B97-1/pVQZ 3.2 d
(9.8)
B3LYP/6-31G(d) 5.2 6.8
(31.5)
B3LYP/6-31+G(d) 5.9
(35.9)
B3LYP/6-311+G(3df,2p) 2.4 3.1 4.8
(9.9) (20.2) (21.6)
B3LYP/aug-cc-pVTZ 2.6
(18.2)
B3LYP/6-311++G(3df,3pd) 3.3 4.2 b 3.1 c 4.9 c
B3LYP/pVQZ 3.4 d
(22.2)
(20.1) (20.8)
B3LYP*/TZVPP 3.0
(11.1)
B3P86/6-31G(d) 5.9
(22.6)
B3P86/6-311+G(3df,2p) 7.8 18.2c 26.1c (22.7) (48.1) (79.2)
B3PW91/6-31G(d,p) 6.8
B3PW91/TZ2P 6.5
B3PW91/6-311+G(3df,2p) 3.5
(21.8)
B3PW91/6-311++G(3df,3pd) 4.8 3.4c 3.9c (21.6) (21.6)
O3LYP/pVQZ 3.9d 4.2e (11.8)
mPW3PW91/6-311++G(3df,3pd) 2.7
(7.4)
X3LYP/6-311+G(3df,2p) 2.8 e
a A: G2 subset (32 molecules containing only first-row atoms, see Johnson, Gill, and Pople 1993); B: G2 set (55
molecules including first- and second-row atoms, see Curtiss et al. 1991); C: (108 molecules including first- and
second-row atoms, see Scheiner, Baker, and Andzelm 1997); D: G2/97 set (148 molecules including first- and
second-row atoms, see Curtiss et al. 1998 and also http://chemistry.anl.gov/compmat/g3theory.htm); E: G3/99
set (223 molecules including first- and second-row atoms, larger organics, and problematic inorganic molecules,
see Curtiss et al. 2000).
b Zero-point-exclusive atomization energies for 109 molecules having high overlap with test set C, MG3S basis set
for DFT values, see Lynch and Truhlar 2003a.
c Geometries and ZPVE obtained at the B3LYP/6-31G(2df,p) level with scaling of vibrational frequencies by 0.9854;
electronic energies use 6-311++G(3df,3pd) basis set; see Staroverov et al. (2003).
d 105 molecules having high overlap with test set C, see Hoe, Cohen, and Handy (2001).
e MP2 geometries and scaled HF thermal contributions; electronic energies use 6-311+G(3df,2p) basis set; see Xu
and Goddard (2004a, 2004b).