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Excited state deactivation pathways of neutral/protonated anisole and p-fluoroanisole: a theoretical study.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Omidyan, Reza Rezaei, Hajar |
| Copyright Year | 2014 |
| Abstract | The potential energy profiles of neutral and protonated anisole and p-fluoroanisole at different electronic states have been investigated extensively by the RI-MP2 and RI-CC2 methods. The calculations reveal that the relaxation dynamics in protonated anisole and p-fluoroanisole are essentially different from those of the neutral analogues. In neutral anisole/p-fluoroanisole, the (1)πσ* state plays a vital relaxation role along the O-CH3 coordinate, yielding the CH3 radical. For both of these molecules, the calculations indicate conical intersections (CIs) between the ground and excited state potential energy (PE) curves, hindered by a small barrier, and providing non-adiabatic gates for radiation-less deactivation to the ground state. Nevertheless, for the protonated cases, besides the prefulvenic deformation of the benzene ring, it has been predicted that the lowest (1)(σ,n)π* state along the C-O-C bond angle plays an important role in photochemistry and the relaxation dynamics. The S1, S0 PE profiles of protonated anisole along with the former reaction coordinate (out-of-plane deformation) show a barrierless relaxation pathway, which can be responsible for the ultrafast deactivation of excited systems to the ground state via the low-lying S1/S0 conical intersection. Moreover, the later reaction coordinate in protonated species (C-O-C angle from 120°-180°) is consequently accompanied with the bond cleavage of C-OCH3 at the (1)(σ,n)π* state, hindered by a barrier of ∼0.51 eV, and can be responsible for the relaxation of excited systems with significant excess energy (hν≥ 5 eV). Furthermore, according to the RI-CC2 calculated results, different effects on the S1-S0 electronic transition energy of anisole and p-fluoroanisole upon protonation have been predicted. The first electronic transitions of anisole and p-fluoroanisole shift by ∼0.3 and 1.3 eV to the red respectively due to protonation. |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/c4cp00679h |
| PubMed reference number | 24810549 |
| Journal | Medline |
| Volume Number | 16 |
| Issue Number | 23 |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/cp/c4/c4cp00679h/c4cp00679h1.pdf |
| Alternate Webpage(s) | http://pubs.rsc.org/en/content/getauthorversionpdf/C4CP00679H |
| Alternate Webpage(s) | https://doi.org/10.1039/c4cp00679h |
| Journal | Physical chemistry chemical physics : PCCP |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
