The intensity of water absorption in the region of the solar spectrum plays a dominant role in atmospheric energy balance and hence strongly influences climate. Significant controversy exists over how to model this absorption accurately. We report dipole moment measurements of highly vibrationally excited water, which provide stringent tests of intensities determined by other means. Our measurements and accompanying calculations suggest that the best currently available potential and dipole surfaces do not accurately model intensities in the optical spectrum of water.
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http://dx.doi.org/10.1126/science.1073731 | DOI Listing |
Phys Chem Chem Phys
January 2025
Department of Chemistry, University of Missouri, Columbia, MO 65211, USA.
We present state-to-state differential cross sections for rotationally inelastic collisions of vibrationally excited NO XΠ ( = 9) with Ar using a near-counterpropagating molecular beam geometry. These were obtained using the stimulated emission pumping technique coupled with velocity map imaging. Collision energies well over ∼1 eV were achieved and rotational excitations up to ∼Δ = 60 recorded for the first time for inelastic collisions.
View Article and Find Full Text PDFACS Phys Chem Au
November 2024
Rosalind Franklin Institute, Harwell OX11 0QX, Oxfordshire, United Kingdom.
Efficient photoredox chemical transformations are essential to the development of novel, cost-effective, and environmentally friendly synthetic methodologies. The concept of the entatic state in bioinorganic catalysis proposes that a preorganized structural configuration can reduce the energy barriers associated with chemical reactions. This concept provides one of the guiding principles to enhance catalytic efficiency by maintaining high-energy conformations close to the reaction's transition state.
View Article and Find Full Text PDFChem Sci
January 2025
University of Strasbourg, CNRS, IPCMS 23 Rue du Loess 67034 Strasbourg France
Archaerhodopsin-3 (AR-3) variants stand out among other rhodopsins in that they display a weak, but voltage-sensitive, near-infrared fluorescence emission. This has led to their application in optogenetics both in cell cultures and small animals. However, in the context of improving the fluorescence characteristics of the next generation of AR-3 reporters, an understanding of their ultrafast light-response in light-adapted conditions, is mandatory.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
Using the time-dependent wave-packet approach, we calculate the first fully converged state-to-state differential cross-sections for the H + HOD( = 1-4) → H + OD reactions on a highly accurate neural network PES. It is found that, unlike the loss of memory effect observed in the product distributions for low vibrational excitation reactions, high initial OH vibrational excitation significantly influences not only the product vibrational distribution but also the angular distribution. Furthermore, for the H + HOD( = 3,4) reactions, the total integral cross-sections maintain the pronounced oscillatory structures in the = 0 probabilities at low collision energies, which originate from the prereactive van der Waals resonances.
View Article and Find Full Text PDFACS Nano
September 2024
Department of Chemistry, Seoul National University, Seoul 08826, Republic of Korea.
Plasmon photocatalysis reactions are thought to occur through vibrationally activated reactants, driven by nonthermal energy transfer from plasmon-induced hot carriers. However, a detailed quantum-state-level understanding and quantification of the activation have been lacking. Using anti-Stokes surface-enhanced Raman scattering (SERS) spectroscopy, we mapped the vibrational population distributions of reactants on plasmon-excited nanostructures.
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