X-ray and Optical Circular Dichroism as Local and Global Ultrafast Chiral Probes of [12]Helicene Racemization

Freixas, Victor M.; Rouxel, Jérémy R.; Nam, Yeonsig; Tretiak, Sergei; Govind, Niranjan; Mukamel, Shaul

doi:10.1021/jacs.3c07032

Title: X-ray and Optical Circular Dichroism as Local and Global Ultrafast Chiral Probes of [12]Helicene Racemization

Journal Article · 13 September 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c07032 · OSTI ID:2305719

^[1]; Rouxel, Jérémy R. ^[2];

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Univ. of California, Irvine, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)

Optical circular dichroism (OCD) is a well-established technique for probing molecular chirality typically in the UV-visible window. Although molecular chirality is usually related to a chiral center, it can alternatively describe a global structure. The electronic transitions are then delocalized and OCD is said to probe the global chirality. Recent advances controlling the polarization and spatial structure of X-ray beams have led to novel spectroscopic techniques such as X-ray circular dichroism (XCD), which can exploit the localized nature of the X-ray electronic transitions. XCD is thus sensitive to local structures and the relevant chirality probed with it can be referred as local. Here, we use the racemization mechanism of the [12]Helicene as a model to assess the capabilities of OCD and XCD as probes of global and local chiralities. In conclusion, our simulations suggest that XCD is a reliable spectroscopic technique for probing the local chirality of molecules, suggesting the further development of this experimental technique.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231; SC0022225; FG02-04ER15571; FWP 72684; FWP LANLE3T1; CHE-2246379

OSTI ID:: 2305719

Report Number(s):: PNNL-SA-186772

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 38; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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