Supporting Information
Reactivity of Molecular Oxygen with Aluminum Clusters:
Density Functional and Ab Initio Molecular Dynamics Simulation
Study
Selvarengan Paranthaman,a,b Jiwon Moon,c Kiryong Hong,a Jeongho Kim,d Dong Eon Kim,b,e
Joonghan Kim,c,* and Tae Kyu Kima,*
a
Department of Chemistry and Chemical Institute for Functional Materials, Pusan National
University, Busan 609-735, Republic of Korea
b
c
Max Plank Center for Attosecond Science, Pohang 790-784, Republic of Korea
Department of Chemistry, The Catholic University of Korea, Bucheon 420-743, Republic of
Korea
d
Department of Chemistry, Inha University, Incheon 402-751, Republic of Korea
e
Department of Physics and Center for Attosecond Science and Technology, POSTECH, Pohang
790-784, Republic of Korea
*
Corresponding Author
(E-mail) tkkim@pusan.ac.kr (T.K. Kim) and joonghankim@catholic.ac.kr (J. Kim)
S1
Figure S1. Optimized molecular structures of a) AlO and b) Al2O2
Figure S2. Optimized molecular structures of Al7− in a) Singlet and b) Triplet states.
S2
Table S1. Al−O bond length (re in Å), vibrational frequency (ωe in cm-1), binding energy (D0 in eV), and difference in ZPE corrected
energy (EZPE=E+ZPE) between 2Π and 2Σ+ states (ΔE=EZPE[2Π] ‒ EZPE[2Σ+], in kcal/mol) for AlO and vertical ionization energy (vIE in eV) for
Al2O2 using the 6-311+G(d) basis set
Molecules
Σ
PBE0
M06-2X
ωB97X
TPSSh
M11
N12-SX
MN12-SX
Exp.
re
1.645
1.637
1.625
1.637
1.641
1.630
1.634
1.652
1.618a
ωe
924.66
941.95
983.59
929.43
949.47
967.60
952.18
899.35
979.23a
D0
4.94
4.78
4.89
4.83
4.89
4.87
5.00
5.01
5.27b
re
1.809
1.801
1.792
1.799
1.809
1.797
1.794
1.797
1.768c
ωe
683.40
697.65
711.55
698.55
687.96
713.87
707.26
698.83
729.70c
11.6
11.0
8.2
8.4
14.1
10.4
12.5
7.7
14.1d
Al2O2
vIE
8.17
8.00
a
Reference 1 (Reference 33 in the main text)
b
Reference 2
c
Reference 3 (Reference 34 in the main text)
d
Reference 4 (Reference 35 in the main text)
e
Reference 5-7
7.81
7.93
7.97
7.80
8.04
8.44
9.9±0.5e
AlO
2 +
Parameters B3LYP
AlO 2Π
ΔE
S3
Table S2. Structural and energetical parameters of isolated Al7− and O2 species: Average Al−Al
bond length (Δr(Al−Al) in Å) in Al7− cluster, vertical spin excitation energy (VSE in eV), adiabatic
spin excitation energy (ASE in eV), and O−O bond length (r(O−O) in Å).
B3LYP
M06-2X
TPSSh
N12-SX
Singlet Triplet Singlet Triplet Singlet Triplet Singlet Triplet
Δr(Al−Al) 2.711 2.743 2.675 2.699 2.680 2.709 2.662 2.686
VSE
0.619
…
0.766
…
0.536
…
0.553
…
ASE
0.156
…
0.508
…
0.080
…
0.118
…
r(O−O)
1.205 1.206 1.187 1.189 1.210 1.209 1.191 1.193
S4
REFERENCES
(1)
K.P. Huber, G. Herzberg, Molecular Spectra and Molecular Structure. IV. Constants of
Diatomic Molecules, Van Nostrand Reinhold Co., New York; 1979.
(2)
T. Andersen, H.K. Haugen, H. Hotop, J. Phys. Chem. Ref. Data 1999, 28, 1511–1533.
(3)
O. Launila, J. Jonsson, J. Mol. Spectrosc. 1994, 168, 1–38.
(4)
B.H. Lengsfield, B. Liu, J. Chem. Phys. 1982, 77, 6083–6089.
(5)
J. Drowart, G. DeMaria, R.P. Burns, M.G. Inghram, J. Chem. Phys. 1960, 32, 1366-1372.
(6)
P. Ho, R.P. Burns, High Temp. Sci. 1980, 12, 31–39.
(7)
C.M. Fu, R.P. Burns,High Temp. Sci. 1976, 8, 353–363.
S5