Explorations of new second-order nonlinear optical materials in the potassium vanadyl iodate system

Article abstract of DOI:10.1021/ja200257a

Four new potassium vanadyl iodates based on lone-pair-containing IO ₃ and second-order Jahn-Teller distorted VO₅ or VO ₆ asymmetric units, namely, α-KVO₂(IO ₃)₂(H₂O) (Pbca), β-KVO₂(IO ₃)₂(H₂O) (P2₁2₁2 ₁), K₄[(VO)(IO₃)₅] ₂(HIO₃)(H₂O)₂ H₂O (P1), and K(VO)₂O₂(IO₃)₃ (Ima2) have been successfully synthesized by hydrothermal reactions. α-KVO ₂(IO₃)₂(H₂O) and β-KVO ₂(IO₃)₂(H₂O) exhibit two different types of 1D [VO₂(IO₃)₂]^- anionic chains. Neighboring VO₆ octahedra in the α-phase are corner-sharing into a 1D chain with the IO₃ groups attached on both sides of the chain in a uni- or bidentate bridging fashion, whereas those of VO₅ polyhedra in the β-phase are bridged by IO₃ groups into a right-handed helical chain with remaining IO₃ groups being grafted unidentately on both sides of the helical chain. The structure of K₄[(VO)(IO₃)₅]₂(HIO ₃)(H₂O)₂ H₂O contains novel isolated [(VO)(IO₃)₅]^2- units composed of one VO ₆ octahedron linked to five IO₃ groups and one terminal O^2- anion. The structure of K(VO)₂O₂(IO ₃)₃ exhibits a 1D [(VO)₂O₂(IO ₃)₃]^- chain in which neighboring VO₆ octahedra are interconnected by both oxo and bridging iodate anions. Most interestingly, three of four compounds are noncentrosymmetric (NCS), and K(VO)₂O₂(IO₃)₃ displays a very strong second-harmonic generation response of about 3.6 × KTP, which is phase matchable. It also has high thermal stability, a wide transparent region and moderate hardness as well as an excellent growth habit. Thermal analyses and optical and ferroelectric properties as well as theoretical calculations have also been performed.(Figure Presented)

Full text of DOI:10.1021/ja200257a

Explorations of New Second-Order NLO Materials in the
Potassium Vanadyl Iodate System
a,b
a
a
a
a
Chuan-Fu Sun, Chun-Li Hu, Xiang Xu, Bing-Ping Yang, Jiang-Gao Mao*
Supporting Information
3 6 5
Table S1. Calculation of dipole moment for IO , VO or VO polyhedra and net
dipole moment for a unit cell in four compounds.
Table S2. The state energies (eV) of the lowest conduction band (L-CB) and the
highest valence band (H-VB) of α-KVO (IO ) (H O), β-KVO (IO ) (H O),
2
3 2
2
2
3 2
2
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
·H
2
O, and K(VO)
2
O
2
3 3
(IO ) .
Table S3. The experimental and calculated gaps as well as the scissor values adopted
in the optical properties calculations.
Table S4. The calculated bond orders of α-KVO
2
(IO
3
)
2
(H
2
O), β-KVO
2
(IO
3
)
2
(H
2
O),
K
4
[(VO)(IO (HIO )(H O) ·H O, and K(VO)
3
)
5
]
2
3
2
2
2
2
O
2
3 3
(IO ) .
Table S5. The angles between the crystallography axes (i.e. a, b and c) and the
principal dielectric axes (i.e. x, y and z) in triclinic crystal
K [(VO)(IO ) ] (HIO )(H O) ·H O.
4
3 5 2
3
2
2
2
Figure S1. Experimental and simulated powder X-ray diffraction data for
α-KVO
2
(IO
3
)
2
(H
2
O), β-KVO
2
(IO
3
)
2
(H
2
O), K
4
[(VO)(IO
3
)
5
2 3 2 2 2
] (HIO )(H O) ·H O,
+
+
+
K(VO) O (IO ) , and M[(VO) (IO ) O ] (M = Rb , Cs , NH ).
2
2
3 3
2
3 3
2
4
S1

Figure S2. Powder X-ray diffraction studies for the thermal decomposition products
of
α-KVO
(HIO )(H O)
Figure S3. The infrared spectra of α-KVO
[(VO)(IO (HIO )(H O) ·H O, and K(VO)
Figure S4. UV absorption spectra of K(VO) (IO
2
(IO
3
)
2
(H
O, and K(VO)
(IO
2
O),
β-KVO
2
(IO
3
)
2
(H
2
O),
K
4
[(VO)(IO
3
)
5
]
2
3
2
2
·H
2
2
O
2
(IO
(H O), β-KVO
(IO
and M[(VO)
3 3
) .
2
3
)
2
2
2
(IO
3
)
2
(H
2
O),
K
4
3
)
5
]
2
3
2
2
2
2
O
2
3 3
) .
2
O
2
3
)
3
2 3 3 2
(IO ) O ] (M =
+
+
+
4
Rb , Cs , NH ).
+
+
2 3 3 2
Figure S5. Optical diffuse reflectance spectra for M[(VO) (IO ) O ] (M = Rb , Cs ,
+
NH ).
4
Figure
S6.
Polarization
(HIO )(H
versus
·H O and K(VO)
(IO (H
O, and K(VO)
applied
electric
(IO
O), β-KVO
(IO
field
for
K
4
[(VO)(IO
3
)
5
]
2
3
2
O)
2
2
2
O
2
3 3
) .
Figure S7. Calculated band structures of α-KVO
[(VO)(IO (HIO )(H O) ·H
2
3
)
2
2
2 3 2 2
(IO ) (H O),
K
4
3
)
5
]
2
3
2
2
2
2
O
2
3 3
) .
Figure S8. Electronic density of states of α-KVO
2
(IO
3
)
2
(H
2
O), β-KVO
2
(IO
3
)
2
(H
2
O),
K [(VO)(IO ) ] (HIO )(H O) ·H O, and K(VO) O (IO ) .
4
3 5 2
3
2
2
2
2
2
3 3
Figure S9. The imaginary part of the dielectric function polarized, average imaginary
part and real part of the dielectric function over three dielectric axes directions
for
β-KVO
2
(IO
3
)
2
(H
2
O),
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
·H
2
O,
and
K(VO) O (IO ) .
2
2
3 3
2 3 2 2
Figure S10. Calculated linear refractive indices for β-KVO (IO ) (H O),
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
·H
2
2 2 3 3
O, and K(VO) O (IO ) .
S2

Figure S11. Calculated frequency-dependent second harmonic generation coefficients
for
β-KVO
2
(IO
3
)
2
(H
2
O),
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
·H
2
O,
and
K(VO)
2
O
2
(IO
3
)
3
.
Figure S12. Calculated frequency-dependent second harmonic generation coefficients
for Rb[(VO) (IO ) O ], Cs[(VO) (IO ) O ], and NH [(VO) (IO ) O ].
2
3 3
2
2
3 3
2
4
2
3 3
2
S3

Table S1. Calculation of dipole moment for IO
3
, VO
6
or VO
5
polyhedra and net
+
dipole moment for a unit cell in four compounds (D = Debyes, K ions and water
molecules were not considered).
α-KVO
2
(IO
3
)
2
(H
2
O)
Dipole moment (D)
Polar unit
total magnitude
x-component
y-component
z-component
I(1)O
I(2)O
V(1)O
3
14.52
14.33
7.64
0
11.63
3.93
1.75
0
8.25
1.51
6.43
0
2.75
13.70
3.74
0
3
6
Net dipole moment (a unit cell)
β-KVO
2
3
(IO )
2
(H
2
O)
Dipole moment (D)
Polar unit
total magnitude
x-component
y-component
z-component
I(1)O
I(2)O
V(1)O
3
14.29
16.59
3.05
0
9.85
15.27
1.75
0
4.94
4.27
0.52
0
9.10
4.89
2.44
0
3
5
Net dipole moment (a unit cell)
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
Dipole moment (D)
x-component y-component
2 2 2
O) ·H O
Polar unit
total magnitude
13.84
13.77
14.53
15.24
15.19
14.64
13.23
16.01
15.75
15.61
14.48
5.34
z-component
3.02
I(1)O
I(2)O
I(3)O
I(4)O
I(5)O
I(6)O
I(7)O
I(8)O
I(9)O
3
3
3
3
3
3
3
3
3
7.19
8.26
10.38
10.22
4.08
11.43
10.93
0.53
11.27
11.51
1.45
1.42
10.15
0.88
9.04
10.44
2.40
10.16
8.67
9.70
7.59
8.05
11.58
0.45
11.96
3.86
9.73
10.24
11.09
9.58
I(10)O
I(11)O
3
10.29
4.81
3
V(1)O
V(2)O
6
2.42
3.33
3.41
3.29
6
5.89
1.97
4.48
Net dipole moment (a unit cell)
33.62
10.21
29.65
12.13
K(VO)
2
O
2
3 3
(IO )
Dipole moment (D)
Polar unit
total magnitude
14.77
x-component
y-component
z-component
2.67
I(1)O
I(2)O
3
0
14.53
4.35
5.36
0
3
13.36
5.86
129.48
1.08
0.71
0
12.59
2.26
129.48
V(1)O
Net dipole moment (a unit cell)
6
S4

Table S2. The state energies (eV) of the lowest conduction band (L-CB) and the
highest valence band (H-VB) of four compounds.
Compound
k-point
L-CB
H-VB
G (0.000, 0.000, 0.000)
Z (0.000, 0.000, 0.500)
T (-0.500, 0.000, 0.500)
Y (-0.500, 0.000, 0.000)
S (-0.500, 0.500, 0.000)
X (0.000, 0.500, 0.000)
U (0.000, 0.500, 0.500)
2.66488
2.66845
2.70478
2.7043
0
-0.01174
-0.14669
-0.14421
-0.25308
-0.16563
-0.18451
-0.25233
-0.01155
-0.01754
-0.07596
-0.07305
-0.0757
0
α-KVO (IO ) (H O)
2
3 2
2
2.74928
2.70825
2.72001
R (-0.500, 0.500, 0.500) 2.74791
G (0.000, 0.000, 0.000)
Z (0.000, 0.000, 0.500)
T (-0.500, 0.000, 0.500)
Y (-0.500, 0.000, 0.000)
S (-0.500, 0.500, 0.000)
X (0.000, 0.500, 0.000)
U (0.000, 0.500, 0.500)
2.53857
2.56016
2.70158
2.69509
2.76193
2.51134
2.51232
β-KVO (IO ) (H O)
2
3 2
2
-5.99739E-4
-0.08197
0
R (-0.500, 0.500, 0.500) 2.76345
G (0.000, 0.000, 0.000)
F (0.000, 0.500, 0.000)
2.00117
1.99736
1.99847
2.001
-0.04061
-0.03874
-0.00593
0
K [(VO)(IO ) ] (HIO )(H O) ·H O Q (0.000, 0.500, 0.500)
4
3 5 2
3
2
2
2
Z (0.000, 0.000, 0.500)
G (0.000, 0.000, 0.000)
T (0.500, -0.500, 0.000)
2.00117
1.83457
-0.06669
-0.24323
-0.08523
-0.09799
-0.00201
W (0.750, -0.250, -0.250) 1.87833
K(VO) O (IO )
3 3
R (0.500, 0.000, 0.000)
G (0.000, 0.000, 0.000)
1.76989
1.96209
2
2
X (0.500, -0.500, -0.500) 1.67255
S5

Table S3. The experimental and calculated gaps as well as the scissor values adopted
in the optical properties calculations.
Eg(exp.)(eV) Eg(cal.) (eV) Scissors (eV)
β-KVO
[(VO)(IO
K(VO) (IO
Rb[(VO) (IO
2
(IO
3
)
2
(H
2
O)
3.39
2.27
2.30
2.35
2.47
2.43
2.51
2.00
1.67
1.61
1.60
1.56
0.88
0.27
0.63
0.74
0.87
0.87
K
4
3
)
5
]
2
(HIO
3 2 2 2
)(H O) ·H O
2
O
2
3 3
)
2
3 3 2
) O ]
Cs[(VO) (IO ) O ]
2
3 3
2
NH
4
[(VO)
2
(IO
3
)
3
O ]
2
Table S4. The calculated bond orders of the four compounds.
α-KVO (IO ) (H O)
2
3
2
2
Bond
V-O
V-O
V-O
I-O
Bond length
1.6283
Bond order
0.91
Bond
V-O
V-O
V-O
I-O
Bond length
1.6613
Bond order
0.80
0.36
0.24
0.38
0.30
0.20
1.9580
0.42
2.0056
2.1832
0.25
2.1735
1.7786
0.48
1.7820
I-O
1.8015
0.37
I-O
1.8633
I-O
1.8188
0.26
I-O
1.8566
2 3 2 2
β-KVO (IO ) (H O)
Bond
V-O
V-O
V-O
I-O
Bond length
1.6186
Bond order
0.93
Bond
V-O
V-O
I-O
Bond length
1.6182
Bond order
0.90
1.9593
0.38
2.0138
0.33
2.02583
1.7769
0.33
1.7748
0.45
0.44
I-O
1.7868
0.44
I-O
1.8328
0.28
I-O
1.8426
0.20
I-O
1.8636
0.18
4 3 5 2 3 2 2 2
K [(VO)(IO ) ] (HIO )(H O) ·H O
Bond
V-O
Bond length
1.5866
Bond order
0.94
Bond
V-O
Bond length
1.5934
Bond order
0.92
S6

V-O
V-O
V-O
V-O
V-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
1.8932
1.8922
1.9144
1.9147
2.1966
1.8082
1.7912
1.8012
1.8084
1.7846
1.8150
1.8035
1.7901
1.8112
1.7980
1.8161
1.8188
1.8592
1.8833
1.8981
1.8599
0.45
0.43
0.42
0.40
0.28
0.56
0.47
0.46
0.44
0.42
0.41
0.40
0.39
0.36
0.35
0.35
0.29
0.23
0.17
0.17
0.15
K(VO)
V-O
V-O
V-O
V-O
V-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
I-O
1.8935
1.8916
1.9202
1.9751
2.1707
1.7903
1.8134
1.7830
1.7969
1.7946
1.8430
1.8046
1.7980
1.7858
1.8111
1.8153
1.8223
1.8870
1.8935
1.8841
1.8671
0.44
0.40
0.41
0.39
0.25
0.47
0.46
0.45
0.43
0.41
0.41
0.40
0.36
0.35
0.35
0.33
0.29
0.21
0.17
0.15
0.12
2
2 3 3
O (IO )
Bond
V-O
V-O
V-O
I-O
Bond length
1.6229
Bond order
0.92
Bond
V-O
V-O
V-O
I-O
Bond length
1.8801
Bond order
0.55
1.8792
0.53
1.9317
0.39
1.9671
0.37
2.2019
0.23
1.7719
0.50
1.7811
0.44
I-O
1.8290
0.29
I-O
1.8485
0.27
I-O
1.8541
0.23
S7

Table S5. The angles between the crystallography axes (i.e. a, b and c) and the
principal dielectric axes (i.e. x, and z) in triclinic crystal
y
K
4
3 5 2 3 2 2 2
[(VO)(IO ) ] (HIO )(H O) ·H O.
a-O-x b-O-x c-O-x a-O-y b-O-y c-O-y a-O-z b-O-z c-O-z
Angle(°) 20.55
74.16
91.52
98.60
36.62 130.50 108.51 57.97
40.54
S8

(
a)
(
b)
(
c)
S9

(
d)
(
e)
(
f)
S10

(
g)
Figure S1. Experimental and simulated powder X-ray diffraction patterns for
α-KVO (IO ) (H O),
β-KVO (IO ) (H O),
4 3 5 2 3 2 2 2
K [(VO)(IO ) ] (HIO )(H O) ·H O,
2
3 2
2
2
3 2
2
+
+
+
K(VO)
2
O
2
(IO
3
)
3
, and M[(VO)
2
(IO
3
)
3
O
2
4
] (M = Rb , Cs , NH ).
S11

(
a)
(
b)
(
c)
S12

(
d)
Figure S2. Powder X-ray diffraction patterns for the thermal decomposition residuals
of α-KVO
2
(IO
3
)
2
(H
2
O) (a), β-KVO
2
(IO
3
)
2
2 4 3 5 2 3
(H O) (b), K [(VO)(IO ) ] (HIO )
(
H
2
O) ·H O (c), and K(VO)
2
2
2
O
2
(IO
3
)
3
(d).
S13

(
a)
(
b)
S14

(
c)
(
d)
Figure S3. The infrared spectra of α-KVO (IO
2
3
)
2
(H
2
2 3 2 2
O) (a), β-KVO (IO ) (H O) (b),
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
·H
2
O (c), and K(VO)
2
O
2
(IO (d).
3 3
)
S15

2 2 3 3 2 3 3 2
Figure S4. UV absorption spectra of K(VO) O (IO ) and M[(VO) (IO ) O ] (M =
+
+
+
Rb , Cs , NH ).
4
S16

+
+
2 3 3 2
Figure S5. Optical diffuse reflectance spectra for M[(VO) (IO ) O ] (M = Rb , Cs ,
+
NH
4
).
S17

Figure
S6.
Polarization
(HIO )(H O) ·H
versus
applied
electric
(b).
field
for
K
4
[(VO)(IO
3
)
5
]
2
3
2
2
2
2 2 3 3
O (a) and K(VO) O (IO )
S18

2 3 2 2 2 3 2 2
Figure S7. Calculated band structures of α-KVO (IO ) (H O) (a), β-KVO (IO ) (H O)
(
b), K [(VO)(IO ) ] (HIO )(H O) ·H O (c), and K(VO) O (IO ) (d) (the Fermi level
4
3 5 2
3
2
2
2
2
2
3 3
is set at 0 eV).
S19

Figure S8. Electronic density of states of α-KVO
2
(IO
3
)
2
(H
2
O) (a),
(IO
β-KVO
2
3
(IO )
2
(H
2
O) (b), K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
2
·H O (c), and K(VO)
2
O
2
3 3
)
(
d).
S20

Figure S9. The imaginary part of the dielectric function polarized along three
dielectric
[(VO)(IO
axes
directions
for
β-KVO
2
(IO
3
)
2
(H
2
O)
(a),
K
4
3
)
5
]
2
(HIO
3
)(H
2
O) ·H O (b), and K(VO)
2
2
2
O
2
3 3
(IO )
(c); and average
imaginary part and real part of the dielectric function over three dielectric axes
directions β-KVO (IO (H O) (d), K [(VO)(IO (HIO )(H O) ·H O (e), and
K(VO) (IO (f).
2
3
)
2
2
4
3
)
5
]
2
3
2
2
2
2
O
2
3 3
)
S21

2 3 2 2
Figure S10. Calculated linear refractive indices for β-KVO (IO ) (H O) (a),
K
4
[(VO)(IO
3
)
5
]
2
(HIO
3
)(H
2
O)
2
·H
2
2 2 3 3
O (b), and K(VO) O (IO ) (c).
S22

Figure S11. Calculated frequency-dependent second harmonic generation coefficients
for β-KVO
2
(IO
3
)
2 2
(H O) (a),
K
4
[(VO)(IO
3
)
5
] (HIO
2
3
)(H
2
O)
2
·H
2
O
(b), and
K(VO) O (IO ) (c).
2
2
3 3
S23

Figure S12. Calculated frequency-dependent second harmonic generation coefficients
for Rb[(VO) (IO ] (a), Cs[(VO) (IO ] (b), and NH [(VO) (IO ] (c).
2
3
)
3
O
2
2
3
)
3
O
2
4
2
3 3 2
) O
S24