Difference in Structure and Electronic Properties of Oxygen Vacancies in α-Quartz and α-Cristobalite Phases of SiO2
Abstract
:1. Introduction
2. Background
2.1. O Vacancy Configurations in SiO
2.2. Properties of -Cristobalite
3. Materials and Methods
4. Results of Calculations
4.1. Pristine Crystals
Parameter | -Cristobalite | -Quartz | ||
---|---|---|---|---|
This Work | Literature Data | This Work | Literature Data | |
Lattice Vectors | ||||
a = b | 5.05 | 4.97 [87] | 4.93 | 4.91 [88] |
c | 7.08 | 6.93 [87] | 5.43 | 5.40 [88] |
Bond length | ||||
Si-O | 1.604–1.609 | 1.600–1.607 [87] | 1.608 | 1.604 [88] |
Si-O | 1.604–1.609 | 1.600–1.607 [87] | 1.612 | 1.613 [88] |
Bond Angles | ||||
O-Si-O | 108–111.8 | 108.1–111.3 [89] | 109.2–110.5 | 109.0–109.5 [88] |
Si-O-Si | 150–153 | 146.6 [87] | 144.8–145.1 | 143.7 [88] |
Density | 2.35 | 2.18–2.37 [44,45] | 2.41 | 2.47–2.70 [44,45,90] |
Band gap | 8.57 | 8.54 [44] | 8.5 | 9.65 [75] |
4.2. Oxygen Vacancies
4.2.1. Geometric Structure and Stability
Neutral Vacancies
Positively Charged Vacancies
Negatively Charged Vacancies
4.2.2. Charge Transition Levels
4.2.3. Optical Absorption
4.2.4. EPR Parameters
5. Discussion and Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
DFT | Density Functional Theory |
-C | -cristobalite |
-Q | -quartz |
a-SiO | Amorphous silicon dioxide |
CT | Charge transition |
ODC | Oxygen deficient center |
EPR | Electron paramagnetic resonance |
Opal-CT | Opal cristobalite tridymite |
LDA | Local density approximation |
GTH | Goedecker-Teter-Hutter |
BFGS | Broyden–Fletcher–Goldfarb–Shanno |
XC | Exchange-correlation |
PBE | Perdew-Burke-Ernzerhof |
ADMM | Auxiliary density matrix method |
TD-DFT | Time-dependent density functional theory |
TC-LRC | Truncated coulomb long-range correction |
NEB | Nudged elastic band |
CI-NEB | Climbing image nudged elastic band |
GGA | Generalized gradient approximation |
HSE | Heyd-Scuseria-Ernzerhof |
VB | Valence band |
CB | Conduction band |
CBM | Conduction band minimum |
CTL | Charge transition level |
TS | Transition state |
OA | Optical absorption |
AE | all-electron |
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Bond | -Cristobalite | -Quartz | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Pristine | Pristine | ||||||||||
Si-Si | 3.11 | 2.38 | 2.88 | 4.59 | 2.39 | 3.09 | 2.41 | 3.00 | 4.45 | 5.38 | 2.47 |
Si-O | 5.31 | 5.54 | 5.22 | 4.83 | 5.63 | 3.66 | 4.10 | 3.71 | 1.83 | 1.84 | 4.07 |
Si-O | 1.61 | 1.61–1.63 | 1.57–1.58 | 1.62–1.63 | 1.67–1.70 | 1.61 | 1.63 | 1.58 | 1.62 | 1.61–1.64 | 1.69–1.73 |
Si-O | 1.61 | 1.62–1.63 | 1.57–1.58 | 1.54–1.55 | 1.67–1.71 | 1.61 | 1.62 | 1.57 | 1.58 | 1.57–1.59 | 1.66–1.68 |
Cutoff Radius (Å) | Phase | Defect | Peak Energy (eV) | Oscillator Strength | Transition Type |
---|---|---|---|---|---|
7.5 | -C | 7.62 | 0.22 | ||
7.72 | 0.20 | ||||
8.13 | 0.16 | ||||
8.4 | 0.13 | ||||
7.56 | 0.12 | ||||
7.72 | 0.11 | * | |||
6.4 | -Q | 6.18 | 0.12 | Si. → deloc. ring | |
2 | -C | 7.86 | 0.27 | ||
7.94 | 0.19 | ||||
8.20 | 0.13 | ||||
8.48 | 0.12 | ||||
6.27 | 0.15 | * | |||
7.86 | 0.12 | ||||
-Q | 6.38 | 0.14 | Si → Si | ||
6.43 | 0.12 | Si. → deloc. ring |
AE Basis | -Quartz (mT) | -Cristobalite (mT) | |||
---|---|---|---|---|---|
Silica | Si | Si | Si | Si | Si |
pcJ-0 | 12.29 | 10.11 | 42.25 | 11.16 | 10.78 |
pcJ-1 | 11.14 | 8.70 | 38.96 | 10.44 | 10.01 |
pcJ-2 | 10.26 | 8.06 | 37.46 | 9.55 | 9.17 |
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Milton, K.L.; Durrant, T.R.; Cobos Freire, T.; Shluger, A.L. Difference in Structure and Electronic Properties of Oxygen Vacancies in α-Quartz and α-Cristobalite Phases of SiO2. Materials 2023, 16, 1382. https://doi.org/10.3390/ma16041382
Milton KL, Durrant TR, Cobos Freire T, Shluger AL. Difference in Structure and Electronic Properties of Oxygen Vacancies in α-Quartz and α-Cristobalite Phases of SiO2. Materials. 2023; 16(4):1382. https://doi.org/10.3390/ma16041382
Chicago/Turabian StyleMilton, Katherine L., Thomas R. Durrant, Teofilo Cobos Freire, and Alexander L. Shluger. 2023. "Difference in Structure and Electronic Properties of Oxygen Vacancies in α-Quartz and α-Cristobalite Phases of SiO2" Materials 16, no. 4: 1382. https://doi.org/10.3390/ma16041382