Conical intersections are known to play a vital role in many photochemical processes. The breakdown of the Born-Oppenheimer approximation in the vicinity of a conical intersection causes exciting phenomena, such as the ultrafast radiationless decay of excited states. The passage of a molecule through a conical intersection creates a coherent superposition of electronic states via nonadiabatic couplings. Detecting this coherent superposition may serve as a direct probe of the conical intersection. In this paper, we theoretically demonstrate the use of coherent spontaneous emission in samples with long-range order for probing the occurrence of a conical intersection in a molecule. Our simulations show that the spectrum contains clear signatures of the created coherent superposition of electronic states. We investigate the bandwidth requirements for the x-ray probes, which influence the observation of coherent superposition generated by the conical intersection.
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http://dx.doi.org/10.1063/5.0180976 | DOI Listing |
Biomimetics (Basel)
January 2025
School of Civil Engineering, Key Laboratory of Concrete and Prestressed Concrete Structures of the Ministry of Education, Southeast University, Nanjing 211189, China.
To develop a new type of biomimetic single-cell and multi-cell energy-absorbing box (tube) featuring conical tubes at the intersection of cell walls, it is necessary to address the issue of large bottom-space requirements in current conical energy-absorbing tubes with superior crashworthiness due to their large semi-apical angles. This study proposes adding corrugations to conical tubes with small semi-apical angles and modifying the bottom by replacing the last one or two inclined corrugations with vertical ones. Finite element simulation results show that, compared to conventional conical tubes, adding corrugations reduces the optimal semi-apical angle of conical tubes by 5°, with the optimal range being 5-10°.
View Article and Find Full Text PDFNat Phys
November 2024
Laboratory of Physical Chemistry, ETH Zürich, Zurich, Switzerland.
A dynamical rearrangement in the electronic structure of a molecule can be driven by different phenomena, including nuclear motion, electronic coherence or electron correlation. Recording such electronic dynamics and identifying its fate in an aqueous solution has remained a challenge. Here, we reveal the electronic dynamics induced by electronic relaxation through conical intersections in both isolated and solvated pyrazine molecules using X-ray spectroscopy.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
The quantum transition state framework was developed to calculate the reaction path-resolved scattering matrix for atom-diatom reactions in hyperspherical (APH) coordinates. This approach allows for simply and directly calculating the reaction path-resolved scattering matrix, especially when the encircling reaction path is negligible. It could be used to determine the reactivities of specific pathways in a chemical reaction, providing insights into phenomena such as geometric phase effects.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, UK.
The ground and excited state electronic structure of the molecular photoswitches quadricyclane and norbornadiene is examined qualitatively and quantitatively. A new custom basis set is introduced, optimised for efficient yet accurate calculations. A number of advanced multi-configurational and multi-reference electronic structure methods are evaluated, identifying those sufficiently accurate and efficient to be used in on-the-fly simulations of photoexcited dynamics.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan.
In this study, the radiative and nonradiative decay pathways from the first singlet excited states (denoted as S) of three bithiophene-fused isoquinolines were investigated by using the mixed-reference spin-flip time-dependent density functional theory approach. These isoquinolines, which are prepared via [2 + 2 + 2] cycloaddition reactions between three types of bithiophene-linked diynes and nitriles, exhibit different fluorescence quantum yields in response to the positions of their sulfur atoms. The decay processes, including the fluorescence emission and internal conversion, were considered.
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