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Structural, Electronic and Optical Properties of Bi2O3 Polymorphs by First-Principles

Calculations for Photocatalytic Water Splitting

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Page 1 of 7 AUTHOR SUBMITTED MANUSCRIPT - MRX-103425.R1

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13 Structural, Electronic and Optical Properties of Bi2O3

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15 Polymorphs by First-Principles Calculations for
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Photocatalytic Water Splitting
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20 N.S. Azhar1,*, M.F.M. Taib1, O.H. Hassan3, 4, M.Z.A. Yahya2, 4, A.M.M. Ali1, 4, *
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22 Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam,
23 Selangor, Malaysia
24 2
Faculty of Defence Science & Technology, Universiti Pertahanan Nasional Malaysia,
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26 57000 Kuala Lumpur, Malaysia
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Department of Industrial Ceramics, Faculty of Art & Design, Universiti Teknologi
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29 4
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MARA, 40450 Shah Alam, Selangor, Malaysia
Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor,
30 Malaysia
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33 * Email: nurulsyahirahazhar93@gmail.com, ammali@salam.uitm.edu.my
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37 Abstract. Crystal structures of α-Bi2O3 and β-Bi2O3 were calculated using Cambridge Serial
38 Total Energy Package (CASTEP) based on the first-principles plane-wave ultrasoft
39 pseudopotential method within local density approximation (LDA) and generalized gradient
40 approximation (GGA) together with Perdew-Burke-Ernzerhof (GGA-PBE) and Perdew-Burke-
41 Ernzerhof revised for solid (GGA-PBEsol). The structural parameter of α- Bi2O3 and β-Bi2O3
42 are in good agreement with previous experimental and theoretical data. All of the polymorphs
43 were calculated for the total density of states (TDOS) and the partial density of states (PDOS) of
44 Bi, O atoms. Density of states exhibits hybridization of Bi 6s and O 2p orbitals and the calculated
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45 charge density profiles exhibit the ionic character in the chemical bonding of this compound.
46 The narrowed band gap (Eg) and red-shift of light absorption edge are responsible for the
47 photocatalytic activity of Bi2O3 for water splitting application. The optical properties such as
48 optical absorption and electron energy loss function were calculated to show the best structure
49 among these polymorphs for the photocatalytic water splitting application.
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52 1. Introduction
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53 The world energy consumption, which was reported in 2008 shows that the energy that had been used
54 has reached a rate of 15TW and expected to be nearly double by the year of 2050 [1]. However,
55 according to Ehsan and Wahid (2016), at the current rate of the fossil fuel consumption, depletion of the
56 reserves fossil fuel resources is expected to be occurred in less than 50 years [2]. One of the possible
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ways to cut the world’s dependency of fossil fuel usage is by developing the hydrogen-based energy. A
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59 potentially feasible way to produce the hydrogen is from water splitting process which combine the solar
60 energy and photocatalysts which also known as the photocatalytic water splitting technique. The main
factors that influence the photocatalyst activity are the structure and crystallinity, band gap energy,
 AUTHOR SUBMITTED MANUSCRIPT - MRX-103425.R1 Page 2 of 7

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6 corrosion resistance, the sacrificial agent/electron donor in the water solution, the operating temperature,
7 the light intensity and also the pH of the solution [3].
8 Among the criteria used in order to improve the photoelectrochemical cell (PEC) water splitting

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9 performance increasing the light absorption ranges can be a potential way to harvest more energy by
10 sunlight absorption from the metal oxide photocatalyst. Titanium dioxide (TiO2) is the most common
11 photocatalyst used in photocatalytic water splitting. TiO2 has been widely studied for its outstanding
12 stability and high photocatalytic activity. However, it can only consume the ultraviolet irradiation which
13 is less than 4% of the solar spectrum range due to its relatively wide band gap (3.2 eV) [4]. This gives a

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14 limitation for its light usage in ultraviolet (UV) region.
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In order to overcome it, a potential semiconductor metal oxide, Bismuth (III) Oxide (Bi2O3) with the
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band gap ranging from 2.1 to 2.8 eV is one of the potential candidates because of its unique
18 characteristics, including adequately high oxidation power of valence hole (~+3.13 V vs normal
19 hydrogen electrode (NHE)) and non-toxic nature as TiO2 [5]. Bi2O3 has five main polymorphic forms
20 denoted by α-Bi2O3 (monoclinic), β-Bi2O3 (tetragonal), γ-Bi2O3 (body-centered cubic), δ-Bi2O3 (cubic)
21 and ω-Bi2O3 (triclinic) [6]. However, there is a very small number of studies reported about the triclinic

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22 ω-Bi2O3 phase either in the experimental work or computational study. Among them, the former four
23 polymorphs were reported most by the experimental work. The α phase is stable at relatively low
24 temperatures, δ phase is only stable at temperature between 729℃ and 825℃ and a large hysteresis has
25 been observed on cooling from a high temperature to room temperatures, with the possible occurrences
26 of two intermediate metastable phases with β or γ phase [7].
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27 For a fundamental understanding, a first-principles approach about the photocatalysts which are α-
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Bi2O3 and β-Bi2O3, for photocatalytic water splitting were calculated by using CASTEP were prepared
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30 to evaluate the structural, electronic properties which are band gap and the Density of States and optical
31 properties such as the absorption coefficient and the electrons energy-loss function of α-Bi2O3 and β-
32 Bi2O3. The results obtained were discussed in this paper.
33
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34 2. Computational Method
35 The calculation of Bi2O3 properties were carried out using Cambridge Serial Total Energy Package
36 (CASTEP) code [8], which is based on the density functional theory (DFT) [9, 10] which uses a total
37 energy plane-wave pseudopotential method within the framework of Kohn-Sham DFT [11]. The
38 exchange-correlation effects were treated within the local density approximation (LDA), generalized
39 gradient approximation with the Perdew-Burke-Ernzerhof (GGA-PBE) and also with generalized
40 gradient approximation with Perdew-Burke-Ernzerhof for solid (GGA-PBEsol) [12]. Special k-points
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sampling integration over the Brillouin zone was employed by using the Monkhorst–Pack scheme [13].
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The cut-off energy of 380.0 eV were applied and the k-point grid of 4x3x3 for α-Bi2O3 and 3x3x4 for
44 β-Bi2O3 were set in Monkhorst-Pack scheme is within the convergence value, The geometrical
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45 optimization set for both α- and β-Bi2O3 were 5.0 x 10-6 eV/atom for total energy, 0.01 eV/Å for
46 maximum force, 0.02 GPa for maximum stress and 0.0005 Å for maximum displacement.
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48 3. Results and Discussion
49
50 3.1 Structural Properties
51 The crystal structure of α-Bi2O3 (monoclinic) structure with space group P21/c and β-Bi2O3 (tetragonal)
52 structure with space group P-421c was visualized in Figure 1(a) and 1(b) respectively. The unit cell of
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53 α-Bi2O3 and β-Bi2O3 contains 20 atoms which consist of 8 bismuth (Bi) atoms and 12 oxygen (O) atoms.
54 The valence atomic configuration for α-Bi2O3 and β-Bi2O3 are 5d10 6s2 6p3 for Bismuth (Bi) and 2s2 2p4
55
for Oxygen (O).
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The lattice parameters of α-Bi2O3 is consistent with the experimental lattice parameters within a few
58 percentage less than 1.2% and for the volume cell less than 1% for α-Bi2O3 and percentage less than 3%
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59 and for the volume cell less than 4% for β-Bi2O3. The lattice parameter for α-Bi2O3 which is calculated
60 from GGA-PBE and for β-Bi2O3 that was calculated from GGA-PBEsol show a good agreement with
the experimental values compared to the other calculated lattice parameters. The cell volume of α-Bi2O3
is larger than the volume of β-Bi2O3 which agreed with the experimental results from both structures.
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10 O
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(a) (b)
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Figure 1. Crystal structure of (a) α-Bi2O3 and (b) β-Bi2O3.
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25 Table 1. Lattice parameters (a, b and c) and volume (V) of α-Bi2O3 calculated with LDA and GGA
26 compared with the experimental values. an
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28 GGA
29 LDA Experiment [14]
30 PW91 PBE PBEsol
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32 a (Å) 5.666 5.869 5.876 5.838 5.840
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b (Å) 7.704 8.127 8.129 7.980 8.150
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35 c (Å)
36 7.158 7.414 7.421 7.331 7.500
37 V (Å3)
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312.45 353.63 354.47 341.53 356.97
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41 Table 2. Lattice parameters (a, b and c) and volume (V) of β-Bi2O3 calculated with LDA and GGA
42 compared with the experimental values.
43 GGA
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LDA Experiment [15]

45 PW91 PBE PBEsol
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47 a (Å)
48 7.451 7.946 7.973 7.707 7.739
49 c (Å) 5.291 5.612 5.615 5.486 5.636
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51 V (Å3) 293.72 354.34 356.94 325.85 337.55
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56 3.2 Electronic Properties
57 One important factor to study about photocatalytic water splitting and the properties of the Bi2O3 as
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the photocatalyst is the band structure. Figure 2 shows the band structure of α- and β-Bi2O3 with different
59
60 functional. Below the fermi level is the conduction band (CB) and above it is known as the valence band
(VB). The bottom of CB have to be more negative than the reduction potential of H+ to H2 (0V vs NHE
at pH 0), while the top of VB should be more positive than the oxidation potential of H2O to O2 (1.23V
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6 vs. NHE) [16]. The calculated band gap for α-Bi2O3 is 2.20 eV and for β-Bi2O3 is 0.97 eV by using
7 GGA-PBE and GGA-PBEsol, respectively. The calculation of the electronic properties are using the
8 best functional for each α- and β-Bi2O3. Figure 2(a) shows that the calculated band gap of α-Bi2O3 by

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9 GGA-PBE give the value of 2.20 eV which is indirect gap where the minimum CB is at G and the top
10 of the VB is at Z. Result for the β-Bi2O3 band gap was shown in figure 2(b). The calculated band gap
11 was 0.97 eV and it is indirect gap where the minimum CB is at G and the maximum VB is near M. The
12 experimental band gap of α- Bi2O3 and β-Bi2O3 are 2.58 eV [17] and 1.45eV [18], respectively.
13
Even though the range between the experimental and the theoretical have slightly different where the

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15 theoretical value are smaller than the experimental value, but the calculated band gaps agreed with
16 previous theoretical report. Therefore, it is not take into account and it will not affect the results’ relative
17 accuracy [19]. The small band gap of theoretical calculation is due to the under-estimation which is
18 explained by the DFT limitation, namely the discontinuity in the exchange-correlation potential. The
19 problem with the small band gap value of the theoretical method can be solved by using DFT+U or DFT
20 hybrid method while the wide band gap can be reduced with doping method in order to get the minimum
21

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value of 1.23 eV so that an overall water splitting can be achieved. Based on the band gap result, β-
22 Bi2O3 are most promising candidate for a wide-range of visible light for photocatalytic applications.
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24 (b)  -Bi2O3 GGA-PBEsol
(a) -Bi2O3 GGA-PBE
25 6
26 6 an
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4
29 4
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32 2
Energy (eV)
Energy (eV)

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34 Eg = 2.20 eV
35 Eg= 0.97 eV
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-2
39 -2

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Y A D E Z A M G Z R X G
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45 Figure 2. Band structures of (a) α-Bi2O3 computed from GGA-PBE and (b) β-Bi2O3 computed
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from GGA-PBEsol.
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51 The partial and total density of states (DOS) were shown in Figure 3 and 4 for α-Bi2O3 and β-Bi2O3
52 respectively. Both were calculated in order to describe the electrons contribution from s and p orbitals
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53 at each energy level that can be occupied. The top VB of α-Bi2O3 and β-Bi2O3 shows a strong
54 hybridization between O 2p and Bi 6s electrons while the bottom of CB which is from 0 to 6 eV is
55 mostly contributed by Bi 6p electrons with a very small contribution from the O 2p electrons. There are
56 no hybridization occur between the range of 0 eV to ~3 eV for α-Bi2O3 and β-Bi2O3 due to the existence
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of band gap in both structures.
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Density of States (e/eV)

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8 Bi6p

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9 4

10 2

11 0
-20 -15 -10 -5 0 5
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Energy (eV)
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Density of States (e/eV) Density of States (e/eV)

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14 O2s
15 15 O2p

16 10

17 5

18 0
-20 -15 -10 -5 0 5
19 Energy (eV)
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21 s

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total
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0
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Energy (eV)
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Figure 3. Partial and total density of states of α-Bi2O3 computed from GGA-PBE for (a) Bi
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and (b) O atoms.
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Density of States (e/eV) Density of States (e/eV)

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32 6 Bi6s
33 Bi6p
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35 2

36 0
-20 -15 -10 -5 0 5
37 Energy (eV)
38 20
39 O2s
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O2p
40 10
41 5
42 0
43 -20 -15 -10 -5 0 5
Energy (eV)
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45 20 s
p
46 15
Total
47 10

48 5

49 0
-20 -15 -10 -5 0 5
50 Energy (eV)
51 Figure 4. Partial and total density of states of β-Bi2O3 computed from GGA-PBE for (a) Bi
52 and (b) O atoms.
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59 3.3 Optical Properties

60 Basically, both α-Bi2O3 and β-Bi2O3 can absorb light that has wavelength in ultraviolet (UV) region and
also a small range of visible light region. This can be seen in Figure 5 which show the graph of absorption
coefficient α(ω) against wavelength for α-Bi2O3 and β-Bi2O3 that had been calculated using the best
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6 functional where for α-Bi2O3 by using GGA-PBE while for β-Bi2O3 is GGA-PBEsol. The absorption
7 coefficient determines how far into a material light of a particular wavelength can penetrate before it is
8 absorbed [20] and can be can be explained by using the equation:

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10 1⁄
𝛼(𝜔) = √2𝜔(√𝜀1 2 (𝜔) + 𝜀2 2 (𝜔) − 𝜀1 (𝜔)) 2
(1)
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where 𝜀1 (𝜔) and 𝜀2 (𝜔) real and imaginary part respectively.

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15 The absorption edge of α-Bi2O3 and β-Bi2O3 occurs at the UV region and a small region of visible light
16 spectra at the wavelength of 200nm to 450nm.
17 The electron energy-loss function L(ω) as shown in Figure 6 is described as the energy lost by an
18 electron passing through a homogeneous dielectric material [21]. The L(ω) spectra of α-Bi2O3 and β-
19 Bi2O3 are differences to each other due to the different in the crystal structure. The α-Bi2O3 structure has
20 a broad peak at 10 eV to 15 eV while β-Bi2O3 only has one sharp peak at ~13 eV. The loss function
21

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spectra can also be explained by the equation:
22
23
24
𝜀2 (𝜔)
25 𝐿(𝜔) =
26 𝜀1 2 (𝜔) + 𝜀2 2 (𝜔)
an (2)
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28
29
30 250000
31 Bi2O3
32 200000 Bi2O3
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34 150000
)
-1

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 () (cm

36 100000
37
38 50000
39
40 0
100 200 300 400 500 600 700 800
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42 Wavelength (nm)

43 Figure 5. Calculated absorption coefficient for α-Bi2O3 and β-Bi2O3.

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46 4.0
47 -Bi2O3
3.5
48  -Bi2O3
3.0
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50 2.5

51
L ( )

2.0
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1.5
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1.0
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55 0.5

56 0.0
57 0 5 10 15 20 25 30
Energy (eV)
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59 Figure 6. Calculated electron energy-loss function of α-Bi2O3 and β-Bi2O3.

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6 4. Conclusion
7 As the conclusion, the results that were obtained from the first-principles calculations on description on
8 the structural, electronic and optical properties of α-Bi2O3 and β-Bi2O3. Functional used for both α-Bi2O3
and β-Bi2O3 were different based on the structural properties’ results. The calculated structural

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10 parameter for α-Bi2O3 using GGE-PBE is in better agreement with the experimental values compared
11 with LDA, GGA-PW9, GGA-PBE and GGA-PBEsol while for β-Bi2O3, GGA-PBEsol is the best
12 functional among others. Both α-Bi2O3 and β-Bi2O3 have an indirect band gap of about 2.20 eV and 0.97
13 eV calculated from GGA-PBE and GGA-PBEsol respectively. Both the valence band and conduction

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14 band contain the contributions from O 2p and Bi 6s, indicating hybridization between these states as
15
observed from the partial and total density of states (DOS). The optical calculations were performed in
16
17
order to see the optical behavior of α-Bi2O3 and β-Bi2O3. The optical absorption was found to be in the
18 range of ultraviolet light (UV) region and also a short range of visible light region. This computational
19 study on α-Bi2O3 and β-Bi2O3 can be used in experimental work to support and verified the results given.
20
21 Acknowledgment

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22 The authors would like to thank Universiti Teknologi MARA (UiTM) and Ministry of Education
23 Malaysia for NRGS, FRGS, ERGS, and RAGS funding this research.
24
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