The influence of quantum mechanics on the dynamics of chemical reactions is unknown for many processes in chemistry. Chemical reaction dynamics are often well described by quasiclassical motion of the atoms on quantum mechanical Born-Oppenheimer potential energy surfaces. Here we present a dynamic isotope effect in a nucleophilic substitution reaction experiment that can only be explained by quasiclassical trajectory simulations for reactants containing deuterium atoms, but not when hydrogen atoms are involved. The calculated energy- and angle-differential cross sections are compared to experimental crossed-beam velocity map imaging data, which show significantly more forward scattering for hydrogenated compared to deuterated reactants. Quantum scattering calculations in reduced dimensions explain this by an increased reaction probability for large total angular momentum, a feature that is not captured in the quasiclassical approach.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11890872 | PMC |
| http://dx.doi.org/10.1038/s41467-025-57086-0 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Isotope-coded hydrazide tags for MALDI-MS based quantitative glycomics.
Talanta
March 2025
The Key Laboratory for Biomedical Photonics of MOE at Wuhan National Laboratory for Optoelectronics, Hubei Bioinformatics & Molecular Imaging Key Laboratory, Systems Biology Theme, Department of Biomedical Engineering, College of Life Science and Technology, Huazhong University of Science and Technology, Wuhan, 430074, China. Electronic address:
The detection of glycosylation alterations is essential for elucidating the roles of glycan functions in biological processes and identifying potential disease biomarkers. Stable isotopic chemical labeling, coupled with mass spectrometry (MS), represents a powerful approach in quantitative glycomics. In this study, we synthesized a novel isotopic hydrazide pair, 2,6-Dimethyl-4-chinolincarbohydrazid (DMQCH) and its deuterium isomer DMQCH-d, via an efficient and cost-effective method, and applied it for the first time in MALDI-MS-based quantitative glycomics.
View Article and Find Full Text PDFThe effects of photosynthetic rate on respiration in light, starch/sucrose partitioning, and other metabolic fluxes within photosynthesis.
Sci Rep
March 2025
MSU-DOE Plant Research Laboratory, Michigan State University, East Lansing, MI, 48824, USA.
In the future, plants may encounter increased light and elevated CO levels. How consequent alterations in photosynthetic rates will impact fluxes in photosynthetic carbon metabolism remains uncertain. Respiration in light (R) is pivotal in plant carbon balance and a key parameter in photosynthesis models.
View Article and Find Full Text PDFTime-efficient approach for environmental transformation and bioavailability assessment of isotopically enriched nanoparticles to increase environmental relevance.
Sci Total Environ
March 2025
Norwegian Institute for Water Research, Oslo, Norway. Electronic address:
The increasing use of engineered nanoparticles (NPs) and their release into the environment requires an assessment of their fate and (eco-) toxicological effects. Previous studies have often focused on pristine NPs or NPs spiked into the effluent of simulated wastewater treatment plants (WWTP) fed with artificial wastewater, combined with unrealistic high exposure concentrations to overcome problems associated with high metal background concentrations. In this study environmentally transformed NPs were obtained by direct spiking into an anaerobic digester filled with municipal sewage sludge.
View Article and Find Full Text PDFPhotoisomerization-mediated tunable pore size in metal organic frameworks for U(VI)/V(V) selective separation.
Nat Commun
March 2025
Frontiers Science Center for Rare Isotopes, School of Nuclear Science and Technology, Lanzhou University, Lanzhou, China.
Selective extracting uranium from seawater is quite challenging, particularly the presence of vanadium, which poses a significant obstacle for most amidoxime absorbents. Adsorbents with size-matched pores and coordination environment can improve the uranium selectivity but usually deteriorate the adsorption capacity. Herein, a dynamically matched spatial coordination strategy is proposed to improve the performance of uranium extraction.
View Article and Find Full Text PDFAccuracy, linearity, and statistical differences in comparative quantification in untargeted plant metabolomics using LC-ESI-Orbitrap-MS.
Anal Bioanal Chem
March 2025
Department of Agrobiotechnology IFA-Tulln, Institute of Bioanalytics and Agro-Metabolomics, BOKU University, Vienna, Tulln, 3430, Austria.
High-resolution mass spectrometers, particularly when paired with liquid chromatography, are the instrument of choice for untargeted metabolomics approaches. Instruments, such as the Orbitrap, offer high sensitivity, selectivity, and exceptional mass accuracy, though they pose certain technical challenges, complicating absolute and comparative quantification. Consequently, method validation is crucial to ensure reliable results, as untargeted metabolomics approaches require the detection and quantification of a large number of metabolites in a broad dynamic range.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!