Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks
<p>Ball-and-stick representation of the building blocks models of the THDB network: (<b>A</b>) model M1, portion of an ideal honeycomb boroxine network, (<b>B</b>) model M2, (<b>C</b>) model M3. B atoms in yellow, O atoms in red, H atoms in white.</p> "> Figure 2
<p>Calculated B K-edge NEXAFS spectrum of THDB (reported on the right side). (<b>Upper panel</b>): DFT-TP results; (<b>lower panel</b>): ΔSCF results. The stick spectra are broadened by using a Gaussian line shape with FWHM = 0.5 eV. ΔSCF B1s IP (197.28 eV) is reported as a vertical dashed line.</p> "> Figure 3
<p>Calculated B1s NEXAFS spectra of M1 (<b>upper panel</b>), M2 (<b>middle panel</b>) and M3 (<b>lower panel</b>) molecular models depicted on the right side. Labels denote the non-equivalent B<sub>i</sub> sites (see text for explanation). Transitions from the non-equivalent B<sub>i</sub> atoms are reported as vertical colored lines in the spectra. The ΔSCF B1s ionization energies are shown as vertical dashed lines (the IP values are reported in <a href="#app1-nanomaterials-12-01610" class="html-app">Supplementary Table S1</a>). The stick spectra are broadened by using a Gaussian line shape with FWHM = 0.3 eV.</p> "> Figure 4
<p>Comparison between the calculated B1s NEXAFS spectra of free M3 (<b>upper panel</b>) and M3@Au(111) (<b>lower panel</b>). The contributions of the three groups of non-equivalent B<sub>i</sub> sites are also shown (colored solid lines). The ΔSCF B1s ionization energies are shown as vertical dashed lines (the IP values are reported in <a href="#app1-nanomaterials-12-01610" class="html-app">Supplementary Table S1</a>). The stick spectra are broadened by using a Gaussian line shape with FWHM = 0.3 eV. The M3 and M3@Au(111) models employed are reported on the right side.</p> "> Figure 5
<p>B1s NEXAFS spectra of boroxinated monolayer ((<b>upper panel</b>), experimental data with permission from ref. [<a href="#B7-nanomaterials-12-01610" class="html-bibr">7</a>]), M3@Au(111) (<b>middle panel</b>) and THBoroxine (<b>lower panel</b>) at the two different polarization angles. For the THBoroxine molecule (displayed along the corresponding spectrum), the B1s total spectrum is also reported. The ΔSCF B1s ionization energies are shown as vertical dashed lines (IP mean value for M3@Au, 198.92 eV for THBoroxine). The calculated stick spectra are broadened by using a Gaussian line shape with FWHM = 0.3 eV.</p> ">
Abstract
:1. Introduction
2. Methods
2.1. Geometry Optimization
2.2. NEXAFS Spectra Calculation
3. Results and Discussion
3.1. THDB Molecule
3.2. M1, M2 and M3 Molecular Models
3.3. M3@Au(111) Model
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Peak | Transition | ΔSCF Results | DFT-TP Results | Assignment, Main Character of the Final MO | ||
---|---|---|---|---|---|---|
E(eV) | f × 102 a | E(eV) | f × 102 a | |||
A | B1s → 5a” | 191.13 | 6.74 | 191.65 | 10.56 | π(B–B) + π*(B–O) |
B | B1s → 15a’ | 193.22 | 0.50 | 194.16 | 0.66 | mixed valence σ*(B–B), σ*(O–H)/Rydberg |
B1s → 16a’ | 193.71 | 0.61 | 194.72 | 0.74 | mixed valence σ*(O–H)/Rydberg | |
C | B1s → 6a” | 194.69 | 1.37 | 195.73 | 5.62 | π*(B–B) + π*(B–O) |
B1s → 7a” | 195.22 | 1.54 | 196.10 | 2.10 | π*(B–B) + π*(B–O) |
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Toffoli, D.; Bernes, E.; Cossaro, A.; Balducci, G.; Stener, M.; Mauri, S.; Fronzoni, G. Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks. Nanomaterials 2022, 12, 1610. https://doi.org/10.3390/nano12091610
Toffoli D, Bernes E, Cossaro A, Balducci G, Stener M, Mauri S, Fronzoni G. Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks. Nanomaterials. 2022; 12(9):1610. https://doi.org/10.3390/nano12091610
Chicago/Turabian StyleToffoli, Daniele, Elisa Bernes, Albano Cossaro, Gabriele Balducci, Mauro Stener, Silvia Mauri, and Giovanna Fronzoni. 2022. "Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks" Nanomaterials 12, no. 9: 1610. https://doi.org/10.3390/nano12091610