Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Vibrationally excited molecular hydrogen production from the water photochemistry

ABSTRACT: Vibrationally excited molecular hydrogen has been commonly observed in the dense photo-dominated regions (PDRs). It plays an important role in understanding the chemical evolution in the interstellar medium. Until recently, it was widely accepted that vibrational excitation of interstellar H2 was achieved by shock wave or far-ultraviolet fluorescence pumping. Here we show a further pathway to produce vibrationally excited H2 via the water photochemistry. The results indicate that the H2 fragments identified in the O(1S) + H2(X1Σg+) channel following vacuum ultraviolet (VUV) photodissociation of H2O in the wavelength range of λ = ~100-112 nm are vibrationally excited. In particular, more than 90% of H2(X) fragments populate in a vibrational state v = 3 at λ~112.81 nm. The abundance of water and VUV photons in the interstellar space suggests that the contributions of these vibrationally excited H2 from the water photochemistry could be significant and should be recognized in appropriate interstellar chemistry models. Understanding the source of vibrationally excited molecular hydrogen is an essential prerequisite for understanding the chemical evolution in the universe. Here the authors report a photodissociation pathway to produce vibrationally excited H2 via the water photochemistry.

SUBMITTER: Chang Y

PROVIDER: S-EPMC8563719 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Excited-state hydrogen atom abstraction initiates the photochemistry of β-2'-deoxycytidine.

Project description:Understanding the effects of ultraviolet radiation on nucleotides in solution is an important step towards a comprehensive description of the photochemistry of nucleic acids and their constituents. Apart from having implications for mutagenesis and DNA photoprotection mechanisms, the photochemistry of cytidines is a central element in UV-assisted syntheses of pyrimidine nucleotides under prebiotically plausible conditions. In this contribution, we present UV-irradiation experiments of β-2'-deoxycytidine in aqueous solution involving H-D exchange followed by NMR spectroscopic analysis of the photoproducts. We further elucidate the outcome of these experiments by means of high-level quantum chemical calculations. In particular, we show that prolonged UV-irradiation of cytidine may lead to H-C1' hydrogen atom abstraction by the carbonyl oxygen atom of cytosine. This process may enable photoanomerisation and nucleobase loss, two previously unexplained photoreactions observed in pyrimidine nucleotides.

| S-EPMC4866440 | biostudies-literature

On the Probability Density of the Nuclei in a Vibrationally Excited Molecule.

Project description:For localized and oriented vibrationally excited molecules, the qualitative features of the one-body probability density of the nuclei (one-nucleus density) are investigated. Like the familiar and widely used one-electron density that represents the probability of finding an electron at a given location in space, the one-nucleus density represents the probability of finding a nucleus at a given position in space independent of the location of the other nuclei and independent of their type. In contrast to the electrons, however, the nuclei are comparably localized. Due to this localization of the individual nuclei, the one-nucleus density provides a quantum-mechanical representation of the "chemical picture" of the molecule as an object that can largely be understood in a three-dimensional space, even though its full nuclear probability density is defined on the high-dimensional configuration space of all the nuclei. We study how the nodal structure of the wavefunctions of vibrationally excited states translates to the one-nucleus density. It is found that nodes do not necessarily lead to visible changes in the one-nucleus density: Already for relatively small molecules, only certain vibrational excitations change the one-nucleus density qualitatively compared to the ground state. It turns out that there are simple rules for predicting the shape of the one-nucleus density from the normal mode coordinates. A Python module for the computation of the one-nucleus density is provided at https://gitlab.com/axelschild/mQNMc.

| S-EPMC6562893 | biostudies-literature

Solvent tuning of photochemistry upon excited-state symmetry breaking.

Project description:The nature of the electronic excited state of many symmetric multibranched donor-acceptor molecules varies from delocalized/multipolar to localized/dipolar depending on the environment. Solvent-driven localization breaks the symmetry and traps the exciton in one branch. Using a combination of ultrafast spectroscopies, we investigate how such excited-state symmetry breaking affects the photochemical reactivity of quadrupolar and octupolar A-(?-D)2,3 molecules with photoisomerizable A-?-D branches. Excited-state symmetry breaking is identified by monitoring several spectroscopic signatures of the multipolar delocalized exciton, including the S2???S1 electronic transition, whose energy reflects interbranch coupling. It occurs in all but nonpolar solvents. In polar media, it is rapidly followed by an alkyne-allene isomerization of the excited branch. In nonpolar solvents, slow and reversible isomerization corresponding to chemically-driven symmetry breaking, is observed. These findings reveal that the photoreactivity of large conjugated molecules can be tuned by controlling the localization of the excitation.

| S-EPMC7174366 | biostudies-literature

Steering Photoelectrons Excited in Carbon Dots into Platinum Cluster Catalyst for Solar-Driven Hydrogen Production.

Project description:In composite photosynthetic systems, one most primary promise is to pursue the effect coupling among light harvesting, charge transfer, and catalytic kinetics. Herein, this study designs the reduced carbon dots (r-CDs) as both photon harvesters and photoelectron donors in combination with the platinum (Pt) clusters and fabricated the function-integrated r-CD/Pt photocatalyst through a photochemical route to control the anchoring of Pt clusters on r-CDs' surface for solar-driven hydrogen (H2) generation. In the obtained r-CD/Pt composite, the r-CDs absorb solar photons and transform them into energetic electrons, which transfer to the Pt clusters with favorable charge separation for H2 evolution reaction (HER). As a result, the efficient coupling of respective natures from r-CDs in photon harvesting and Pt in proton reduction is achieved through well-steered photoelectron transfer in the r-CD/Pt system to cultivate a remarkable and stable photocatalytic H2 evolution activity with an average rate of 681 µmol g-1 h-1. This work integrates two functional components into an effective HER photocatalyst and gains deep insights into the regulation of the function coupling in composite photosynthetic systems.

| S-EPMC5737228 | biostudies-literature

Panoramic portrait of primary molecular events preceding excited state proton transfer in water.

Project description:Photochemistry powers numerous processes from luminescence and human vision, to light harvesting. However, the elucidation of multidimensional photochemical reaction coordinates on molecular timescales remains challenging. We developed wavelength-tunable femtosecond stimulated Raman spectroscopy to simultaneously achieve pre-resonance enhancement for transient reactant and product species of the widely used photoacid pyranine undergoing excited-state proton transfer (ESPT) reaction in solution. In the low-frequency region, the 280 cm-1 ring deformation mode following 400 nm photoexcitation exhibits pronounced intensity oscillations on the sub-picosecond timescale due to anharmonic vibrational coupling to the 180 cm-1 hydrogen-bond stretching mode only in ESPT-capable solvents, indicating a primary event of functional relevance. This leads to the contact ion pair formation on the 3 ps timescale before diffusion-controlled separation. The intermolecular 180 cm-1 mode also reveals vibrational cooling time constants, ?500 fs and 45 ps in both H2O and D2O, which differ from ESPT time constants of ?3/8 and 90/250 ps in H2O/D2O, respectively. Spectral results using H218O further substantiate the functional role of the intermolecular 180 cm-1 mode in modulating the distance between proton donor and acceptor and forming the transient ion pair. The direct observation of molecular structural evolution across a wide spectral region during photochemical reactions enriches our fundamental understanding of potential energy surface and holds the key to advancing energy and biological sciences with exceptional atomic and temporal precision.

| S-EPMC6021748 | biostudies-literature

Methanol photo-reforming with water on pure titania for hydrogen production.

Project description:The behaviour of titania for the photo-reforming of methanol with water at ambient temperature has been examined. It is shown that the reactivity is very poor, compared with metal-loaded catalysts at low methanol levels in solution, but the rate becomes much higher at high methanol levels, such that the difference from metal-loaded samples is much less. The optimum yield is with approximately a 1 : 1 methanol/water solution. The reaction also proceeds well in the gas phase. During all such catalysis, the titania becomes blue, due to light absorption increasing across the range 400-800 nm. However, this does not result in visible range activity for the photo-reforming and is due to the reduction of the material in the presence of light and the formation of anion vacancies and Ti3+ centres. These anion vacancies are only very slowly re-oxidized in air on P25 titania, taking days to recover the original whiteness of the oxide. The performance of anatase, rutile and the mixed phase is compared. This article is part of a discussion meeting issue 'Science to enable the circular economy'.

| S-EPMC7422889 | biostudies-literature

Boosting photocatalytic hydrogen production from water by photothermally induced biphase systems.

Project description:Solar-driven hydrogen production from water using particulate photocatalysts is considered the most economical and effective approach to produce hydrogen fuel with little environmental concern. However, the efficiency of hydrogen production from water in particulate photocatalysis systems is still low. Here, we propose an efficient biphase photocatalytic system composed of integrated photothermal-photocatalytic materials that use charred wood substrates to convert liquid water to water steam, simultaneously splitting hydrogen under light illumination without additional energy. The photothermal-photocatalytic system exhibits biphase interfaces of photothermally-generated steam/photocatalyst/hydrogen, which significantly reduce the interface barrier and drastically lower the transport resistance of the hydrogen gas by nearly two orders of magnitude. In this work, an impressive hydrogen production rate up to 220.74 μmol h-1 cm-2 in the particulate photocatalytic systems has been achieved based on the wood/CoO system, demonstrating that the photothermal-photocatalytic biphase system is cost-effective and greatly advantageous for practical applications.

| S-EPMC7910610 | biostudies-literature

Molecular orbital analysis of the hydrogen bonded water dimer.

Project description:As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond's O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of hydrogen bonding in ice, liquid water, functional materials and biological systems.

| S-EPMC4764947 | biostudies-literature

Mapping molecular orientation with phase sensitive vibrationally resonant sum-frequency generation microscopy.

Project description:We demonstrate a phase sensitive, vibrationally resonant sum-frequency generation (PSVR-SFG) microscope that combines high resolution, fast image acquisition speed, chemical selectivity, and phase sensitivity. Using the PSVR-SFG microscope, we generate amplitude and phase images of the second-order susceptibility of collagen I fibers in rat tail tendon tissue on resonance with the methylene vibrations of the protein. We find that the phase of the second-order susceptibility shows dependence on the effective polarity of the fibril bundles, revealing fibrous collagen domains of opposite orientations within the tissue. The presence of collagen microdomains in tendon tissue may have implications for the interpretation of the mechanical properties of the tissue.

| S-EPMC3966429 | biostudies-literature