| Full text | |
| Author(s): |
Total Authors: 2
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| Affiliation: | [1] Univ Sao Paulo, Dept Quim & Fis Mol, Inst Quim Sao Carlos, Ave Trabalhador Sao Carlense 400, CP 780, BR-13560970 Sao Carlos, SP - Brazil
Total Affiliations: 1
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| Document type: | Journal article |
| Source: | Journal of Molecular Structure; v. 1246, DEC 15 2021. |
| Web of Science Citations: | 0 |
| Abstract | |
Polyoxoniobates are polyoxometalates with applications in catalysis, water splitting and organic reactions such as condensation of Knoevenagel and Cycloaddition of CO2. Actually, range-separated hybrids (RSHs) are being indicated for the description of electronic excitations within Time Dependent Density Func-tional Theory (TDDFT), mainly in systems presenting charge - transfer transitions. Here, this protocol is applied for studying ultraviolet - visible (UV/Vis) bands of polyoxoniobates in aqueous solution. Al-though the experimental data for comparison are scarce, the RSHs investigated were particularly suc-cessful, providing wavelength deviations usually smaller than 30 nm. Results indicate that wavelengths change slightly among all these compounds (22 - 35 nm), with the following sequence: {[}Nb10O28](6-) < {[}Nb6O19]8- < {[}SiNb12O40](16-) = {[}AsNb12O40](15-) = {[}PNb12O40](15-) < {[}GeNb12O40](16-). Atomic charges in internal oxygens and heteroatoms are nearly insensitive to these transitions. In addition, the largest elec-tronic charge transfer from oxygens to niobium occurs in {[}Nb6O19](8-) (0.39 e ), followed by {[}Nb10O28](6-) (0.31 e ), {[}SiNb12O40](16-) (0.27 e ), {[}PNb12O40](15-) (0.23 e ), {[}AsNb12O40](15-) (0.11 e ) and {[}GeNb12O40](16-) (0.06 e ). (C) 2021 Elsevier B.V. All rights reserved. (AU) | |
| FAPESP's process: | 14/23714-1 - Electronic structure relativistic calculations for evaluation of new prolapse-free basis sets |
| Grantee: | Roberto Luiz Andrade Haiduke |
| Support Opportunities: | Regular Research Grants |