Quantum Mechanical Modeling of the Vibrational Spectra of Minerals with a Focus on Clays
Abstract
:1. Introduction
2. Theory and Terminology
2.1. Frequencies
2.2. Intensities
2.3. Bandwidths
2.4. Anharmonicity
3. Practical Considerations
4. Examples
4.1. Gibbsite
- Gibbsite D [58]3623 3526 3456 3397 3367 3290 1054 1020 967 942 915
- DFT bulk gibbsite3673 3666 3549 3526 3508 3494 1119 1086 1058 1041 1010 990
- DFT (001) surface gibbsite3866 3835 3759 3736 3668 3522 3475 1110 1066 1027 994
4.2. Birnessites
4.3. Kaolinite–Acetic Acid
4.4. Silica Species in SiO2–H2O Liquids and Glass
4.5. Further Reading
5. Conclusions
- Make sure you are building a model that represents reality as closely as possible.
- Search the literature for previous studies for guidance as to which method will be accurate for your purposes.
- Use periodic and cluster models to complement one another; each model type has strengths and weaknesses.
- Most classical force field methods will not be as accurate as quantum methods. Many are parameterized to have bond force constants, k, obtained from experimental vibrational frequencies.
- Benchmark computational methods against well-understood systems wherever possible to estimate error in calculations.
- If possible, compare your calculated results with other sources of experimental data (e.g., NMR, XANES, EXAFS) to increase the certainty of your calculated results.
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Mode | ν(Harm) (cm−1) | ν(Anharm) (cm−1) |
---|---|---|
Fundamental Bands | ||
1(1) | 3913.897 | 3726.279 |
2(1) | 3800.402 | 3628.674 |
3(1) | 1664.814 | 1615.055 |
Overtones | ||
1(2) | 7827.794 | 7355.593 |
2(2) | 7600.805 | 7172.676 |
3(2) | 3329.628 | 3193.999 |
Combination Bands | ||
2(1) 1(1) | 7714.299 | 7190.895 |
3(1) 1(1) | 5578.711 | 5324.089 |
3(1) 2(1) | 5465.217 | 5233.679 |
ZPE(Harm) = 56.10 kJ/mol ZPE(Anharm) = 55.24 kJ/mol |
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Kubicki, J.D.; Watts, H.D. Quantum Mechanical Modeling of the Vibrational Spectra of Minerals with a Focus on Clays. Minerals 2019, 9, 141. https://doi.org/10.3390/min9030141
Kubicki JD, Watts HD. Quantum Mechanical Modeling of the Vibrational Spectra of Minerals with a Focus on Clays. Minerals. 2019; 9(3):141. https://doi.org/10.3390/min9030141
Chicago/Turabian StyleKubicki, James D., and Heath D. Watts. 2019. "Quantum Mechanical Modeling of the Vibrational Spectra of Minerals with a Focus on Clays" Minerals 9, no. 3: 141. https://doi.org/10.3390/min9030141