Modeling Dynamic Conformations of Organic Molecules: Alkyne Carotenoids in Solution
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60076658%3A12310%2F20%3A43901161" target="_blank" >RIV/60076658:12310/20:43901161 - isvavai.cz</a>
Alternative codes found
RIV/60077344:_____/20:00525260 RIV/61388971:_____/20:00525260
Result on the web
<a href="https://pubs.acs.org/doi/full/10.1021/acs.jpca.9b11536" target="_blank" >https://pubs.acs.org/doi/full/10.1021/acs.jpca.9b11536</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jpca.9b11536" target="_blank" >10.1021/acs.jpca.9b11536</a>
Alternative languages
Result language
angličtina
Original language name
Modeling Dynamic Conformations of Organic Molecules: Alkyne Carotenoids in Solution
Original language description
Calculating the spectroscopic properties of complex conjugated organic molecules in their relaxed state is far from simple. An additional complexity arises for flexible molecules in solution, where the rotational energy barriers are low enough so that nonminimum conformations may become dynamically populated. These metastable conformations quickly relax during the minimization procedures preliminary to density functional theory calculations, and so accounting for their contribution to the experimentally observed properties is problematic. We describe a strategy for stabilizing these nonminimum conformations in silico, allowing their properties to be calculated. Diadinoxanthin and alloxanthin present atypical vibrational properties in solution, indicating the presence of several conformations. Performing energy calculations in vacuo and polarizable continuum model calculations in different solvents, we found three different conformations with values for the delta dihedral angle of the end ring ca. 0, 180, and 90 degrees with respect to the plane of the conjugated chain. The latter conformation, a nonglobal minimum, is not stable during the minimization necessary for modeling its spectroscopic properties. To circumvent this classical problem, we used a Car-Parinello MD supermolecular approach, in which diadinoxanthin was solvated by water molecules so that metastable conformations were stabilized by hydrogen-bonding interactions. We progressively removed the number of solvating waters to find the minimum required for this stabilization. This strategy represents the first modeling of a carotenoid in a distorted conformation and provides an accurate interpretation of the experimental data.
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
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2020
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 Physical Chemistry A
ISSN
1089-5639
e-ISSN
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Volume of the periodical
124
Issue of the periodical within the volume
14
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
2792-2801
UT code for WoS article
000526394300008
EID of the result in the Scopus database
2-s2.0-85083084244