Details

Autor(en) / Beteiligte

• Gromov, Evgeniy V
• Burghardt, Irene
• Köppel, Horst
• Cederbaum, Lorenz S

Titel

Impact of Sulfur vs Oxygen on the Low-Lying Excited States of trans-p-Coumaric Acid and trans-p-Coumaric Thio Acid

Ist Teil von

• The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2005-05, Vol.109 (20), p.4623-4631

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2005

Quelle

MEDLINE

Beschreibungen/Notizen

• The low-lying excited singlet states of trans-p-coumaric acid (CA) and trans-p-coumaric thio acid (CTA) are investigated in view of characterizing the chromophore of the photoactive yellow protein (PYP), with particular regard to the impact of sulfur on the chromophore's electronic structure. The comparative ab initio study, performed with the highly accurate EOM-CCSD method, shows that the electronic state ordering upon vertical excitation and following in-plane geometry relaxation indeed depends in a very sensitive fashion on the presence of either sulfur or oxygen. The study identifies three relevant excited singlet states, two of which are of π−π* type while the third state is of n−π* character. The study highlights the role of the latter n−π* state which is shown to be the lowest-lying excited state of CTA at all in-plane geometries under consideration, whereas this is not the case for CA.