Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT
Abstract
:1. Introduction
2. Computational Models and DFT Calculations Details
3. Results and Discussion
3.1. Models of Ternary Systems MgCl/TiCl/EB
3.2. Adsorption Properties of Adducts on MgCl Nanoplatelets
3.3. IR and Raman Response of EB/TiCl on Nanoplatelet
3.3.1. IR Simulations
- the (C=O) vibration that dominates the IR spectrum and is located at 1683, 1697 and 1695 cm for models A–C, downshifted by 83, 69 and 71 cm in reference to gas phase, respectively. Two very weak satellite bands are also osberved at 1638 and 1615 cm that correspond to C-C stretching modes of the phenyl ring. In the presence of a TiClEB adduct (model D) the C=O stretching mode undergoes a huge redshift to 1587 cm (medium); it is further redshifted to 1556 cm and coupled with a very weak band at 1585 cm in the case of adduct E: they correspond to the antisymmetric and to the symmetric coupling of the two C=O stretchings;
- the (C-O) signal drops its intensity with respect to free EB and is splitted into three components at 1308, 1323, 1336; 1312, 1332, 1348 and 1313, 1329, 1344 cm for models A–C, respectively due to coupling with CH twisting and phenyl H modes; however for model A the triplet of bands have comparable intensity, whereas for model B and C the band at higher wavenumber dominates in the triplet. A similar group of bands is observed for models D and E with the most intense peak located at 1362 cm;
- a new weak band appears at 1414, 1418, 1417 cm for models A–C, and at 1427 cm for models D–E, is associated to the wagging of -CH and therefore slightly perturbed by different EB binding mode; the band is weak but it can be clearly identified in the IR spectra;
- in the spectral region 400–500 cm region, for A and B models the Ti-Cl stretching mode at 465 and 485 cm are only slightly perturbed by the presence of EB; for model C, the coupling with EB mode causes the splitting of Ti-Cl symmetric stretching mode in components at 464, 465, 468 cm and antisymmetric Ti-Cl stretching at 483, 484, also partially coupled with Mg-Cl modes of tetrahedral Mg at 490 cm. For models D–E two further bands, not visible in Raman, pop-up at 437 cm and at 449 cm due to bending modes of O-Ti-O and Ti-O-C, respectively. Weak bands at 588, 645 cm assigned to Ti-O-C appear.
3.3.2. Raman Characterization MgCl/TiCl/EB Adducts
3.4. Discussion
3.5. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Acknowledgments
Conflicts of Interest
References
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Reaction | Model | E (B3LYP-D2) | E (M06) |
---|---|---|---|
EB + (MgClTiCl) → (MgClTiClEB) | A | −79.3 | −81.6 |
“ | B | −78.9 | −80.9 |
” | C | −77.5 | −79.5 |
TiClEB + (MgClTiCl) → (MgClTiClEB) | D | −66.3 | −75.4 |
TiClEB + (MgClTiCl) → (MgClTiClEB) | E | −181.2 | −185.8 |
EB + (MgClTiCl) → ((MgClTiClEB) | F | −99.3 | −96.0 |
TiClEB + (MgClTiCl) → (MgClTiClEB) | G | −79.3 | −94.9 |
TiClEB + (MgClTiCl) → (MgClTiClEB) | H | −172.1 | −191.6 |
TiClEB + (MgClTiCl) → (MgClTiClEB) | I | −79.5 | −95.3 |
EB + (MgClTiClEB) → (MgClTiClEB) | J | −121.9 | −123.6 |
(MgClTiClEB) → (MgClTiClEB) | G | 35.5 | 60.9 |
(MgClTiClEB) → (MgClTiClEB) | H | 55.5 | 67.8 |
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D’Amore, M.; Taniike, T.; Terano, M.; Ferrari, A.M. Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT. Materials 2022, 15, 909. https://doi.org/10.3390/ma15030909
D’Amore M, Taniike T, Terano M, Ferrari AM. Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT. Materials. 2022; 15(3):909. https://doi.org/10.3390/ma15030909
Chicago/Turabian StyleD’Amore, Maddalena, Toshiaki Taniike, Minoru Terano, and Anna Maria Ferrari. 2022. "Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT" Materials 15, no. 3: 909. https://doi.org/10.3390/ma15030909