Rotational circular dichroism of diamagnetic and paramagnetic molecules. A computational study
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F23%3A00573984" target="_blank" >RIV/61388963:_____/23:00573984 - isvavai.cz</a>
Alternative codes found
RIV/60461373:22340/23:43926517
Result on the web
<a href="https://doi.org/10.1063/5.0156273" target="_blank" >https://doi.org/10.1063/5.0156273</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1063/5.0156273" target="_blank" >10.1063/5.0156273</a>
Alternative languages
Result language
angličtina
Original language name
Rotational circular dichroism of diamagnetic and paramagnetic molecules. A computational study
Original language description
Rotational circular dichroism (RCD) has not been observed yet, but it is expected to deliver information about chiral molecules useful in many branches of chemistry. In the past, rather weak RCD intensities were predicted for model diamagnetic molecules and a limited number of rotational transitions. Here, we review quantum-mechanical foundations and simulate entire spectral profiles, including larger molecules, open-shell molecular radicals, and high-momentum rotational bands. Contribution of the electric quadrupolar moment was considered, but it turned out that it does not contribute to field-free RCD. Two conformers of a model dipeptide provided clearly distinct spectra. The dissymmetry Kuhn parameter gK predicted for the diamagnetic molecules even for high-J transitions rarely exceeded 10−5, and the simulated RCD spectra were often biased to one sign. In the radicals, the coupling of the rotational angular momentum with the spin for some transitions raised gK to about 10−2, and the RCD pattern was more conservative. In the resultant spectra, many transitions had negligible intensities due to small populations of the involved states, and a convolution with a spectral function made the typical RCD/absorption ratios about 100-times smaller (gK ∼ 10−4). This is still comparable with values typical for electronic or vibrational circular dichroism, and paramagnetic RCD is thus likely to be measurable relatively easily.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA22-33060S" target="_blank" >GA22-33060S: Instrumentation and theory for measurement of terahertz optical activity of biomolecules</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Physics
ISSN
0021-9606
e-ISSN
1089-7690
Volume of the periodical
159
Issue of the periodical within the volume
2
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
024115
UT code for WoS article
001027283200002
EID of the result in the Scopus database
2-s2.0-85164401150