Ab initio studies of two pyrimidine derivatives as possible photo-switch systems

• Authors: András Csehi , Clemens Woywod , Gábor Halász , Ágnes Vibók
• Languages of publication: EN

Abstracts

EN

The six lowest lying electronic singlet states of 8-(pyrimidine-2-yl)quinolin-ol and 2-(4-nitropyrimidine-2-yl)ethenol have been studied theoretically using the complete active space self-consistent-field (CASSCF) and M’ller-Plesset second-order perturbation theory (MP2) methods. Both molecules can be viewed as consisting of a frame and a crane component. As a possible mechanism for the excited-state relaxation process an intramolecular hydrogen transfer promoted by twisting around the covalent bond connecting the molecular frame and crane moieties has been considered. Based on this idea we have attempted to derive abstracted photochemical pathways for both systems. Geometry optimizations for the construction of hypothetical reaction coordinates have been performed at the MP2 level of theory while the CASSCF approach has been employed for the calculation of vertical excitation energies along the pathways. The results of the calculations along the specific twisting displacements investigated in this study do not support the notion of substantial twisting activity upon excitation of any of the five excited states at the planar terminal structures of the torsion coordinates of both molecules. However, the present analysis should be considered only as a first, preliminary step towards an understanding of the photochemistry of the two candidate compounds. For example, we have not performed any excited state geometry optimizations so far and the estimates of vertical excitation energies do not take dynamical electron correlation into account. Further work on this subject is in progress.

Keywords

EN

ab initio calculations; molecular switches; electronic states; pyrimidine derivatives

• Publisher: De Gruyter Open
• Journal: Open Physics
• Year: 2013
• Volume: 11
• Issue: 9
• Pages: 1141-1148

Dates

published

1 - 9 - 2013

online

24 - 11 - 2013

Contributors

author

András Csehi

• Department of Information Technology, University of Debrecen, H-4010, Debrecen, PO Box 12, Hungary

author

Clemens Woywod

• Centre for Theoretical and Computational Chemistry, Chemistry Department, University of Tromsø, N-9037, Tromsø, Norway

author

Gábor Halász

• Department of Information Technology, University of Debrecen, H-4010, Debrecen, PO Box 12, Hungary

author

Ágnes Vibók

• Department of Theoretical Physics, University of Debrecen, H-4010, Debrecen, PO Box 5, Hungary

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Identifiers

DOI

10.2478/s11534-013-0174-8