TY  - GEN
A1  - Schönborn, Jan Boyke
A1  - Hartke, Bernd
T1  - Photochemical dynamics of E-methylfurylfulgide
BT  - kinematic effects on photorelaxation dynamics of furylfulgides
N2  - With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 237 
KW  - decay dynamics
KW  - fulgides
KW  - implementation
KW  - molecular-dynamics
KW  - photoinduced nonadiabatic dynamics
KW  - photoisomerization
KW  - ring-closure
KW  - semiempirical methods
KW  - spectroscopy
KW  - state
Y1  - 2013
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-94516
SP  - 2483
EP  - 2490
ER  - 
TY  - GEN
A1  - Matis, Jochen René
A1  - Schönborn, Jan Boyke
A1  - Saalfrank, Peter
T1  - A multi-reference study of the byproduct formation for a ring-closed dithienylethene photoswitch
N2  - Photodriven molecular switches are sometimes hindered in their performance by forming byproducts which act as dead ends in sequences of switching cycles, leading to rapid fatigue effects. Understanding the reaction pathways to unwanted byproducts is a prerequisite for preventing them. This article presents a study of the photochemical reaction pathways for byproduct formation in the photochromic switch 1,2-bis-(3-thienyl)-ethene. Specifically, using single- and multi-reference methods the post-deexcitation reaction towards the byproduct in the electronic ground state S0 when starting from the S1–S0 conical intersection (CoIn), is considered in detail. We find an unusual low-energy pathway, which offers the possibility for the formation of a dyotropic byproduct. Several high-energy pathways can be excluded with high probability.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 215 
Y1  - 2015
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89594
SP  - 14088
EP  - 14095
ER  -