A Density Functional Theory Study of Optical Rotation in some Aziridine and Oxirane derivatives

Research output: Contribution to journalJournal articleResearchpeer-review

  • Ramiro S. Galeano Carrano
  • Patricio F. Provasi
  • Marta B. Ferraro
  • Ibon Alkorta
  • José Elguero
  • Sauer, Stephan P. A.
We present time-dependent density functional theory (TDDFT) calculations of the electronic optical rotation (ORP) for seven oxirane and two aziridine derivatives in the gas phase and in solution and compare the results with the available experimental values. For seven of the studied molecules it is the first time that their optical rotation was studied theoretically and we have therefore investigated the influence of several settings in the TDDFT calculations on the results. This includes the choice of the one-electron basis set, the exchange-correlation functional or the particular polarizable continuum model (PCM). We can confirm that polarized quadruple zeta basis sets augmented with diffuse functions are necessary for converged results and find that the aug-pc-3 basis set is a viable alternative to the frequently employed aug-cc-pVQZ basis set. Based on our study, we cannot recommend the generalized gradient functional KT3 for calculations of the ORP in these compounds, whereas the hybrid functional PBE0 gives results quite similar to the long-range correct CAM-B3LYP functional. Finally, we observe large differences in the solvent effects predicted by the integral equation formalism of PCM and the SMD variant of PCM. For the majority of solute/solvent combinations in this study, we find that the SMD model in combination with the PBE0 functional and the aug-pc-3 basis set gives the best agreement with the experimental values.
Original languageEnglish
JournalChemPhysChem
Volume22
Issue number8
Pages (from-to)764-774
Number of pages11
ISSN1439-4235
DOIs
Publication statusPublished - 21 Apr 2021

    Research areas

  • Faculty of Science - optical rotation, density functional theory (DFT), solvent effects, Basis sets

ID: 255886910