Ultrafast non-adiabatic dynamics of excited diphenylmethyl bromide elucidated by quantum dynamics and semi-classical on-the-fly dynamics
Physical Chemistry Chemical Physics, ISSN: 1463-9076, Vol: 20, Issue: 35, Page: 22753-22761
2018
- 11Captures
Metric Options: Counts1 Year3 YearSelecting the 1-year or 3-year option will change the metrics count to percentiles, illustrating how an article or review compares to other articles or reviews within the selected time period in the same journal. Selecting the 1-year option compares the metrics against other articles/reviews that were also published in the same calendar year. Selecting the 3-year option compares the metrics against other articles/reviews that were also published in the same calendar year plus the two years prior.
Example: if you select the 1-year option for an article published in 2019 and a metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019. If you select the 3-year option for the same article published in 2019 and the metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019, 2018 and 2017.
Citation Benchmarking is provided by Scopus and SciVal and is different from the metrics context provided by PlumX Metrics.
Example: if you select the 1-year option for an article published in 2019 and a metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019. If you select the 3-year option for the same article published in 2019 and the metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019, 2018 and 2017.
Citation Benchmarking is provided by Scopus and SciVal and is different from the metrics context provided by PlumX Metrics.
Metrics Details
- Captures11
- Readers11
- 11
Article Description
Carbocations and carboradicals are key intermediates in organic chemistry. Typically UV laser excitation is used to induce homolytical or heterolytical bond cleavage in suitable precursor molecules. Of special interest hereby are diphenylmethyl compounds (PhCH-X) with X = Cl, Br as a leaving group as they form diphenylmethyl radicals (PhCH) and cations (PhCH) within a femtosecond time scale in polar solvents. In this work, we build on our methodology developed for the chlorine case and investigate the photodissociation reaction of PhCH-Br by state-of-the-art theoretical methods. On the one hand, we employ specially adapted reactive coordinates for a grid-based wave packet dynamics in reduced dimensionality using the Wilson G-matrix ansatz for the kinetic part of the Hamiltonian. On the other hand, we use full-dimensional semiclassical on-the-fly dynamics with Tully's fewest switches surface hopping routine for comparison. We apply both methods to explain remarkable differences in experimental transient absorption measurements for Cl or Br as the leaving group. The wave packet motion, visible only for the bromine leaving group, can be related to the crucial role of the central carbon atom, which undergoes rehybridization from sp to sp during the photoinduced bond cleavage. Comparable features are the two consecutive conical intersections near the Franck-Condon region controlling the product splitting to PhCH/Br and PhCH/Br as well as the difference in delay time for the respective product formation.
Bibliographic Details
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=85053295854&origin=inward; http://dx.doi.org/10.1039/c8cp03257b; http://www.ncbi.nlm.nih.gov/pubmed/30140797; https://xlink.rsc.org/?DOI=C8CP03257B; https://dx.doi.org/10.1039/c8cp03257b; https://pubs.rsc.org/en/content/articlelanding/2018/cp/c8cp03257b
Royal Society of Chemistry (RSC)
Provide Feedback
Have ideas for a new metric? Would you like to see something else here?Let us know