Molecular dynamics and metadynamics simulations of [2 + 2] photocycloaddition

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00500251" target="_blank" >RIV/61388955:_____/18:00500251 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1002/qua.25534" target="_blank" >http://dx.doi.org/10.1002/qua.25534</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/qua.25534" target="_blank" >10.1002/qua.25534</a>

Result language

angličtina

Original language name

Molecular dynamics and metadynamics simulations of [2 + 2] photocycloaddition

Original language description

Triplet state mechanism of [2 + 2] photocycloaddition forming a cyclobutane ring from two ethylenes is investigated in the context of photocatalysis. High‐level ab initio calculations are combined with ab initio adiabatic molecular dynamics and ab initio metadynamics for rare events modeling. In a photocatalytic scheme, a reactant reaches the triplet state either via intersystem crossing (ISC) or triplet sensitization. The model system adopts a biradical structure, which represents energy intersection with the ground state. The system either completes cyclization or undergoes fragmentation into two olefinic units. The potential and free energy surfaces of the cyclobutane/ethylenes system are mapped with multireference approaches describing possible reaction pathways. To obtain a full picture of a double bond photoreactivity, ab initio adiabatic dynamical calculations were used to estimate reaction yields and to model the effects of excess energy. The potential use of density functional theory based approaches for [2 + 2] photocycloaddition was investigated for future simulations and design of realistic photocatalytic systems. Dynamical aspects of [2 + 2] photocycloaddition via a triplet state manifold are investigated by combining ab initio multireference methods and ab initio molecular dynamics and metadynamics. The reaction pathways are studied for a model system of two ethylenes forming a cyclobutane ring to provide a basis for further studies on design of photocatalytic systems.n

Czech name

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Czech description

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Type

J_imp - 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

Project

<a href="/en/project/GA17-04068S" target="_blank" >GA17-04068S: Molecular Clusters as Unique Nano-reactors: Controlling Chemistry with Photons and Electrons</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2018

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

International Journal of Quantum Chemistry

ISSN

0020-7608

e-ISSN

—

Volume of the periodical

118

Issue of the periodical within the volume

10

Country of publishing house

US - UNITED STATES

Number of pages

11

Pages from-to

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UT code for WoS article

000429003500004

EID of the result in the Scopus database

2-s2.0-85044826356