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Data for Determination of secondary species in solution through pump-selective transient absorption spectroscopy and explicit-solvent TDDFT
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Turner, M. A. P., Horbury, Michael D., Stavros, Vasilios G. and Hine, Nicholas (2019) Data for Determination of secondary species in solution through pump-selective transient absorption spectroscopy and explicit-solvent TDDFT. [Dataset]
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Official URL: https://doi.org/10.5281/zenodo.1483226
Abstract
The measured electronic excitations of a given species in solution are often a composite of the electronic excitations of various equilibrium species of that molecule. It is common for a proportion of a species to deprotonate in solution, or form a tautomeric equilibrium, producing new peaks corresponding to the electronic excitations of the new species. One prominent example is alizarin in methanol, which at different temperatures, and in solutions with differing pH, has an isosbestic point between the two dominant excitations at 435 and 540 nm. The peak at 435 nm has been attributed to alizarin; the peak at 540 nm, however, more likely results from a species in equilibrium with alizarin. In this work, we were able to use both experimental and computational techniques to selectively examine electronic properties of both alizarin and its secondary species in equilibrium. This was achieved through use of transient electronic absorption spectroscopy, following selective photoexcitation of a specific species in equilibrium. The resulting transient electronic absorption spectra were compared to the known transient absorption spectra of potential secondary equilibrium species. The ground state absorption spectra associated with each species in equilibrium were predicted using linear-scaling time-dependent density functional theory with an explicitly modeled solvent and compared to the experimental result. This evidence from both techniques combines to suggest that the excitation at 540 nm arises from a specific monoanionic form of alizarin.
Item Type: | Dataset | |||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TP Chemical technology |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics |
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Library of Congress Subject Headings (LCSH): | Alizarin, Methanol , Density functionals | |||||||||||||||||||||
Journal or Publication Title: | The Journal of Physical Chemistry A | |||||||||||||||||||||
Publisher: | University of Warwick, Department of Chemistry ; University of Warwick, Department of Physics | |||||||||||||||||||||
ISSN: | 1089-5639 | |||||||||||||||||||||
Official Date: | 8 January 2019 | |||||||||||||||||||||
Dates: |
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DOI: | 10.1021/acs.jpca.8b11013 | |||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||
Media of Output (format): | .dat .out .xyz .nw .csv | |||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||
Description: | Data is linked at Zenodo. "explicit" - These are explicit-solvent calculations of excited states of alizarin in MeOH using the PBE functional - Files contain results for alizarin-a; alizarin-b; monoanion-a; and monoanion-b "implicit" - These are implicit-solvent calculations of alizarin in MeOH using aug-cc-pVTZ and implicit methanol - Functionals include PBE/PBE0/B3LYP/CAM-B3LYP/LS-PBE0 "monoanion_b_rotation" These are the implicit solvent calculations for the rotation around a dihedral angle in monoanion-b - opt_ are restricted geometry optimizations in the electronic ground state (PBE0/cc-pVTZ) "transient_electronic_absorption_spectrometry" - Raw TEAS results for alizarin in methanol at pH = 3,7,9 with pumps at 425 nm and 550 nm -_transients_ denotes results for TEAS |
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Date of first compliant deposit: | 23 January 2019 | |||||||||||||||||||||
RIOXX Funder/Project Grant: |
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