Supplementary Material
Photoelectron Spectroscopy and Theoretical Study of M(IO3)2–
(M = H, Li, Na, K): Structural Evolution, Optical Isomers and
Hyperhalogen Behavior
Gao-Lei Hou,1,2,a) Miao Miao Wu,3 Hui Wen,2,a) Qiang Sun,4,b) Xue-Bin Wang,2,b)
Wei-Jun Zheng1,b)
1
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of
Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, China
2
Physical Sciences Division, Pacific Northwest National Laboratory, P. O. Box 999,
MS K8-88, Richland, Washington 99352, USA
3
Department of Materials Science and Engineering, China University of Mining and
Technology (Beijing), Beijing 100083, China
4
Department of Materials Science and Engineering and Center for Applied Physics
and Technology, Peking University, Beijing 100871, China
b)
AUTHOR EMAIL ADDRESS: xuebin.wang@pnnl.gov; zhengwj@iccas.ac.cn;
sunqiang@pku.edu.cn
a)
Visiting students via PNNL alternate sponsored fellowship. Permanent address for
H.W.: Laboratory of Atmospheric Physical Chemistry, Hefei Institutes of Physical
Sciences, Chinese Academy of Sciences (CAS), Hefei, Anhui 230031, China.
1
IO3
VDE (eV): 4.77 (expt.)
4.65 (B3LYP)
5.07(0.925)(OVGF)
Anion
HIO3
Neutral
HIO3 crystal
I—O: 1.81, 1.89, 1.80 Å
H—O: 1.01 Å (corresponding
I—O: 1.89 Å)
LiIO3
LiIO3 crystal
I—O: 1.80 Å (average)
Li—O: 2.08 Å
NaIO3
NaIO3 crystal
I—O: 1.802, 1.811, 1.811 Å
Na—O: 2.40 Å (average)
KIO3
KIO3 crystal
I—O: 1.794, 1.807, 1.844 Å
K—O: 2.887 Å (average)
FIG. S1. The optimized most stable geometries of IO3– and its corresponding neutral,
MIO3 (M = H, Li, Na, K). Selected bond lengths (in Å) are indicated, and the
parameters determined from the corresponding crystal structures are also given in the
right column.
2
Anion
Neutral
a
a′
b
b′
FIG. S2. The optimized most stable geometries of Na(ClO3)2– and its corresponding
neutral. Two energetically degenerate optical isomers are given. Isomer b is the
structure obtained by Anusiewice. Selected bond lengths (in Å) and their comparison
with those obtained by Anusiewice (in blue bold) are indicated.
3
HOMOs
LUMOs
H-a
H-b
Li-a
Li-b
Na-a
Na-b
K-a
K-b
FIG. S3 The highest occupied molecular orbitals (HOMOs) and lowest unoccupied
molecular orbitals (LUMOs) of the M(IO3)2– (M = H, Li, Na, K).
4
Anions
Neutrals
H-a
H-b
Li-a
Li-b
Na-a
Na-b
5
K-a
K-b
FIG. S4. Natural bond orbital (NBO) charge distributions of M(IO3)2– (M = H, Li, Na,
K) and their corresponding neutrals.
6
TABLE S1. Reported ADEs and VDEs of MX2– (M = Li, Na, K; X = F, Cl, Br, I)
superhalogen anions.
–
LiF2
LiCl2–
LiBr2–
LiI2–
NaF2–
NaCl2–
NaBr2–
NaI2–
KF2–
KCl2–
a
ADE (eV)
5.45c
4.97c
5.12c
4.69c
4.2c
VDE (eV)
c
6.51
5.92(4)[5.90]a; 5.88c
5.42(3)[5.48]a
4.88(3)[4.57]a
6.18c
5.86(6)[5.81]a; 5.77c
5.36(6)[5.43]a
4.84(6)[4.50]a
6.07d
5.37d
J. Chem. Phys. 110, 4763 (1999). Numbers in parentheses indicate the experimental
uncertainty in the last digits and numbers in brackets are from ab initio outer valence
Green function (OVGF) calculations.
b
J. Chem. Phys. 111, 504 (1999).
c
J. Chem. Phys. 107, 3867 (1997).
d
J. Chem. Phys. 99, 441 (1993).
7
TABLE S2. A state-to-state comparison for each M(IO3)2 neutral molecule (M = H,
Li, Na, K) using OVGF calculations and Koopmans’ approximation (the reordered
states are highlighted).
OVGF
H
Li
VDEs(PS)
OV/Koopmans’
Na
K
VDE1
6.526(0.917)
7.466
6.878(0.921)
7.673
6.859(0.923)
7.640
6.773(0.924)
7.547
VDE2
7.010(0.918)
7.956
6.927(0.922)
7.719
6.905(0.923)
7.678
6.816(0.924)
7.583
VDE3
7.464(0.927)
8.837
7.610(0.930)
8.794
7.612(0.933)
8.812
7.721(0.934)
8.889
VDE4
7.628(0.928)
8.992
7.640(0.932)
8.970
7.636(0.933)
8.822
7.740(0.934)
8.881
VDE5
7.706(0.933)
8.904
7.700(0.930)
8.831
7.686(0.933)
8.967
7.745(0.934)
8.910
VDE6
7.711(0.931)
9.074
7.722(0.931)
8.923
7.735(0.933)
8.961
7.505(0.935)
8.753
VDE7
8.005(0.933)
9.355
7.825(0.933)
9.065
7.840(0.934)
8.977
7.530(0.935)
8.761
VDE8
8.205(0.936)
9.879
7.932(0.935)
9.097
7.909(0.936)
9.014
7.767(0.935)
8.924
VDE9
8.299(0.926)
9.506
8.196(0.931)
9.672
8.298(0.935)
9.756
8.278(0.938)
9.734
8