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Table 11.2 The adsorption energies (eV) for CO on Pt 7–3 by using several wavefunction theories
(WFT) and density functional theories (DFT)
Level
Method
E TOP
E FCC
E TOP–FCC
WFT
MP2
−2.70
−2.79
0.09
WFT
HF
−1.09
−0.86
−0.23
Hybrid
M06HF
−1.62
−1.48
−0.14
Hybrid
BMK
−2.68
−2.46
−0.22
Hybrid
M052X
−1.93
−2.47
0.54
Hybrid
wB97
−1.83
−1.22
−0.61
Hybrid
M062X
−1.76
−1.35
−0.41
Hybrid
wB97X
−1.85
−2.28
0.43
Hybrid
BHandH
−2.70
−3.12
0.42
Hybrid
BHandHLYP
−1.78
−1.89
0.11
Hybrid
B1B95
−1.88
−2.46
0.58
Hybrid
B3LYP
−1.50
−1.83
0.33
Hybrid
PBE0
−1.82
−2.49
0.67
Hybrid
B3PW91
−1.64
−2.20
0.56
Hybrid
HSE03
−1.76
−2.38
0.62
Hybrid
HSE06
−1.77
−2.35
0.58
mGGA
M06L
−1.56
−2.00
0.44
GGA
BP86
−1.64
−1.91
0.27
GGA
B97D
−2.24
−2.27
0.03
GGA
PW91
−1.81
−2.18
0.37
GGA
PBE
−1.79
−2.17
0.38
GGA
BLYP
−1.26
−1.38
0.12
LDA
SVWN
−2.76
−3.48
0.72
11.3.3 The CO Adsorption on Pt Clusters
Table 11.2 collects the adsorption energies of CO on Pt 7–3 for HF, MP2 and 21 different level density functional theories. It is found that HF method predicts CO adsorption favoring at top site than at fcc site. However, the MP2 method predicts that
the adsorption strengths at both sites are almost the same. For the LDA (SVWN),
it can be found that the CO strongly favors to adsorb at fcc site than at top site,
and the predicted adsorption energies are strongly overestimated compared to the
experimental value of ca. 1.0–1.3 eV at top site.
For the GGA and meta-GGA, the adsorption energies and energy differences between top and fcc sites are both reduced comparing with these obtained at LDA
level. Among these functionals, the energy differences between top and fcc sites for