Investigating the Effects of Electron Correlation and Methylation on the S 1/S 0 Conical Intersection Seam of Fulvene
Javier Segarra-Martí, Michael J. Bearpark
TL;DR
This paper studies how electron correlation and methylation affect the conical intersection seam of fulvene, a molecule important for understanding radiationless decay processes.
Contribution
The study introduces a detailed comparison of electron correlation effects and methylation impacts on fulvene's conical intersection seam using advanced computational methods.
Findings
Methylation does not significantly alter the energetics of the conical intersection seam in fulvene.
Single methylation (6MFulv) allows easier access to the planar region of the seam compared to parent fulvene or DMF.
DMF is suggested as a suitable experimental surrogate system for testing predictions on fulvene's excited state reactivity.
Abstract
The benzene isomer fulvene has established itself as a computational benchmark for characterizing conical intersections of potential energy surfaces and modeling radiationless decay. However, in contrast to other benchmark systems such as benzene itself or the DNA/RNA nucleobases, there is as yet no time-resolved experimental data for fulvene to compare computational predictions with. This article has three main aims. The first is to thoroughly characterize the S 1/S 0 conical intersection seam of fulvene mediating ultrafast decay along its main reaction coordinates. The second is to understand how radiationless decay is shaped by the electron correlation included in the model and is carried out by comparing XMS-CASPT2 with CASSCF results and extracting how dynamic correlation effects impact differently the critical points encountered along the seam. The third and final aim is to…
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Taxonomy
TopicsCyclization and Aryne Chemistry · Synthesis and characterization of novel inorganic/organometallic compounds · DNA Repair Mechanisms