Theoretical Chemistry Accounts, Год журнала: 2025, Номер 144(6)
Опубликована: Май 24, 2025
Язык: Английский
The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown
Опубликована: Янв. 23, 2025
Understanding and controlling molecular motions is of pivotal importance for designing machinery functional systems, capable performing complex tasks. Herein, we report a comprehensive theoretical study to elucidate the dynamic behavior bis(benzoxazole)-based overcrowded alkene displaying several coupled uncoupled motions. The benzoxazole moieties give rise 4 different stable conformers that interconvert through single-bond rotations. By excited- ground-state dynamics simulations, DFT calculations, NMR studies, found photochemical E-Z isomerization central double bond each conformer directional leads mixture metastable isomers. This transformation analogous classical Feringa-type motors, with notable difference that, during subsequent thermal helix inversion (THI) steps, multiple possible pathways take place involve rotations can be both rotation naphthyl half molecule.
Язык: Английский
Процитировано
0
Nature Communications, Год журнала: 2025, Номер 16(1)
Опубликована: Янв. 30, 2025
Abstract Crystalline pentacene is a model solid-state light-harvesting material because its quantum efficiencies exceed 100% via ultrafast singlet fission. The fission mechanism in crystals disputed due to insufficient electronic information time-resolved experiments and intractable mechanical calculations for simulating realistic crystal dynamics. Here we combine multiscale multiconfigurational approach machine learning photodynamics understand competing mechanisms crystalline pentacene. Our simulations reveal coexisting charge-transfer-mediated coherent the channels herringbone parallel dimers. predicted time constants (61 33 fs) are excellent agreement with (78 35 fs). trajectories highlight essential role of intermolecular stretching between monomers generating multi-exciton state explain anisotropic phenomenon. machine-learning-photodynamics resolved elusive interplay structure vibrational relations, enabling fully atomistic excited-state dynamics quality
Язык: Английский
Процитировано
0
The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown
Опубликована: Фев. 17, 2025
Bithiophene has an electron-rich conjugated ring, enabling highly tunable photophysical properties for the design of novel organic light-emitting materials. Extensive research was focused on functionalization α-site-connected bithiophene, while recent work reported synthesis β-bithiophene, substantially enlarging chemical space bithiophene design. However, rule modulating physical β-bithiophene remained unexplored. We performed comprehensive quantum calculations to investigate how functional groups and substituent sites control absorption emission wavelengths β-bithiophene. Our results show that lead red-shifts by extending electron delocalization, substitution have fewer effects wavelengths. The calculation trithiophene tetrathiophene suggest thiophene polymer are controlled short chains, underscoring significance rational derivatives.
Язык: Английский
Процитировано
0
Bulletin of the Korean Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Март 18, 2025
Abstract Quantum chemical theories are essential tools for predicting the properties of complex quantum systems without need prior empirical data. While traditional have long dominated field, their applicability is often limited in scenarios, particularly involving excited states. Mixed‐Reference Spin‐Flip Time‐Dependent Density Functional Theory (MRSF‐TDDFT) addresses these challenges, offering a robust, accurate, and computationally efficient framework studying both ground states large molecular systems. MRSF‐TDDFT achieves predictive accuracy on par with much more intensive methods. Notably, it successfully describes doubly states, limitation conventional TDDFT, by naturally incorporating key configurations within its response space. This capability also enables to accurately reproduce correct asymptotic behavior bond‐breaking potential energy surfaces. Furthermore, resolves critical photochemical features, such as conical intersections, which elude TDDFT Complete Active Space Self‐Consistent Field (CASSCF) Despite advanced power, retains computational efficiency comparable TDDFT. With development custom‐tailored functionals, can be further enhanced, extending applications. innovation represents significant advancement, empowering researchers uncover intricate behaviors facilitate design novel materials unprecedented precision.
Язык: Английский
Процитировано
0
The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 4315 - 4325
Опубликована: Апрель 23, 2025
Molecular switches based on the norbornadiene-quadricyclane (NBD-QC) isomer pair are among most promising candidates for applications in molecular solar thermal energy storage (MOST). In these compounds, is captured through a photoinduced [2 + 2] cycloaddition reaction whose mechanism only partially understood. This holds true especially NBD derivatives containing type of push-pull substitution pattern that was previously proven necessary to attain reasonable photoisomerization quantum yields. present contribution, we report computational investigation photochemistry NBD-QC with precisely such pattern. Static calculations provide information structures excited electronic states involved reaction, and topographies relevant ground- excited-state potential surfaces. Furthermore, nonadiabatic dynamics (NAMD) simulations allow an estimation time scale yield. The simulation results paint detailed picture capture process: begins spectroscopically bright state switch. model compound which performed NAMD simulations, ring closing takes place roughly 150 fs, makes it one fastest known reactions.
Язык: Английский
Процитировано
0
Theoretical Chemistry Accounts, Год журнала: 2025, Номер 144(6)
Опубликована: Май 24, 2025
Язык: Английский
Процитировано
0