Resumé
| Originalsprog | Engelsk |
|---|---|
| Tidsskrift | Chemical Physics |
| Vol/bind | 328 |
| Udgave nummer | 1-3 |
| Sider (fra-til) | 205-215 |
| Antal sider | 11 |
| ISSN | 0301-0104 |
| DOI | |
| Status | Udgivet - 2006 |
Citer dette
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Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone. / Gorski, Alexander; Posokhov, Yevgen; Hansen, Bjarke Knud Vilster; Spanget-Larsen, Jens; Jasny, Jan; Duus, Fritz; Hansen, Poul Erik; Waluk, Jacek.
I: Chemical Physics, Bind 328, Nr. 1-3, 2006, s. 205-215.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review
TY - JOUR
T1 - Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone
AU - Gorski, Alexander
AU - Posokhov, Yevgen
AU - Hansen, Bjarke Knud Vilster
AU - Spanget-Larsen, Jens
AU - Jasny, Jan
AU - Duus, Fritz
AU - Hansen, Poul Erik
AU - Waluk, Jacek
PY - 2006
Y1 - 2006
N2 - Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.
AB - Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.
KW - Photochromism
KW - Thioxoketones
KW - Linear Dichroism
KW - Polarization Spectroscopy
KW - Matrix Isolation
U2 - 10.1016/j.chemphys.2006.06.033
DO - 10.1016/j.chemphys.2006.06.033
M3 - Journal article
VL - 328
SP - 205
EP - 215
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 1-3
ER -