Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Observation of different reactivities of para and ortho-water towards trapped diazenylium ions.

ABSTRACT: Water is one of the most fundamental molecules in chemistry, biology and astrophysics. It exists as two distinct nuclear-spin isomers, para- and ortho-water, which do not interconvert in isolated molecules. The experimental challenges in preparing pure samples of the two isomers have thus far precluded a characterization of their individual chemical behavior. Capitalizing on recent advances in the electrostatic deflection of polar molecules, we separate the ground states of para- and ortho-water in a molecular beam to show that the two isomers exhibit different reactivities in a prototypical reaction with trapped diazenylium ions. Based on ab initio calculations and a modelling of the reaction kinetics using rotationally adiabatic capture theory, we rationalize this finding in terms of different rotational averaging of ion-dipole interactions during the reaction.

SUBMITTER: Kilaj A

PROVIDER: S-EPMC5974139 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Observation of different reactivities of para and ortho-water towards trapped diazenylium ions.

Kilaj Ardita A Gao Hong H Rösch Daniel D Rivero Uxia U Küpper Jochen J Willitsch Stefan S

Nature communications 20180529 1

Water is one of the most fundamental molecules in chemistry, biology and astrophysics. It exists as two distinct nuclear-spin isomers, para- and ortho-water, which do not interconvert in isolated molecules. The experimental challenges in preparing pure samples of the two isomers have thus far precluded a characterization of their individual chemical behavior. Capitalizing on recent advances in the electrostatic deflection of polar molecules, we separate the ground states of para- and ortho-water ...[more]

PMID: 29844308

Similar Datasets

Electrical detection of ortho-para conversion in fullerene-encapsulated water.

Project description:Water exists in two spin isomers, ortho and para, that have different nuclear spin states. In bulk water, rapid proton exchange and hindered molecular rotation obscure the direct observation of two spin isomers. The supramolecular endofullerene H2O@C60 provides freely rotating, isolated water molecules even at cryogenic temperatures. Here we show that the bulk dielectric constant of this substance depends on the ortho/para ratio, and changes slowly in time after a sudden temperature jump, due to nuclear spin conversion. The attribution of the effect to ortho-para conversion is validated by comparison with nuclear magnetic resonance and quantum theory. The change in dielectric constant is consistent with an electric dipole moment of 0.51±0.05 Debye for an encapsulated water molecule, indicating the partial shielding of the water dipole by the encapsulating cage. The dependence of bulk dielectric constant on nuclear spin isomer composition appears to be a previously unreported physical phenomenon.

| S-EPMC4560827 | biostudies-literature

Quantum rotation of ortho and para-water encapsulated in a fullerene cage.

Project description:Inelastic neutron scattering, far-infrared spectroscopy, and cryogenic nuclear magnetic resonance are used to investigate the quantized rotation and ortho-para conversion of single water molecules trapped inside closed fullerene cages. The existence of metastable ortho-water molecules is demonstrated, and the interconversion of ortho-and para-water spin isomers is tracked in real time. Our investigation reveals that the ground state of encapsulated ortho water has a lifted degeneracy, associated with symmetry-breaking of the water environment.

| S-EPMC3420201 | biostudies-literature

Unusual Reactivities of <i>ortho</i>-Hydroxy-β-nitrostyrene.

Project description:Nitrostyrene derivatives are widely used in organic syntheses as a substrate for Michael addition, photoisomerization and cycloaddition. In contrast, ortho-hydroxy derivatives exhibit unusual behaviors in these reactions. Conjugate addition proceeded upon treatment of the ortho-hydroxy-β-nitrostyrene with an amine; however, subsequent C-C bond cleavage readily occurred to afford the corresponding imine. Moreover, conversion of the trans-isomer to a cis-isomer did not occur efficiently, even when UV light was irradiated. We studied these unusual behaviors of β-nitrostyrene, focusing on the role of the ortho-hydroxy group.

| S-EPMC9369901 | biostudies-literature

Quantum absorption refrigerator with trapped ions.

Project description:In recent years substantial efforts have been expended in extending thermodynamics to single quantum systems. Quantum effects have emerged as a resource that can improve the performance of heat machines. However in the fully quantum regime their implementation still remains a challenge. Here, we report an experimental realization of a quantum absorption refrigerator in a system of three trapped ions, with three of its normal modes of motion coupled by a trilinear Hamiltonian such that heat transfer between two modes refrigerates the third. We investigate the dynamics and steady-state properties of the refrigerator and compare its cooling capability when only thermal states are involved to the case when squeezing is employed as a quantum resource. We also study the performance of such a refrigerator in the single shot regime made possible by coherence and demonstrate cooling below both the steady-state energy and a benchmark set by classical thermodynamics.

| S-EPMC6331551 | biostudies-literature

Experimental observation of quantum oscillation of surface chemical reactivities.

Project description:Here we present direct observation of a quantum reactivity with respect to the amounts of O(2) adsorbed and the rates of surface oxidation as a function of film thickness on ultrathin (2-6 nm) Pb mesas by scanning tunneling microscopy. Simultaneous spectroscopic measurements on the electronic structures reveal a quantum oscillation that originates from quantum well states of the mesas, as a generalization of the Fabry-Pérot modes of confined electron waves. We expect the quantum reactivity to be a general phenomenon for most ultrathin metal films with broad implications, such as nanostructure tuning of surface reactivities and rational design of heterogeneous catalysts.

| S-EPMC1874227 | biostudies-literature

Coordination nano-space as stage of hydrogen ortho-para conversion.

Project description:The ability to design and control properties of nano-sized space in porous coordination polymers (PCPs) would provide us with an ideal stage for fascinating physical and chemical phenomena. We found an interconversion of nuclear-spin isomers for hydrogen molecule H2 adsorbed in a Hofmann-type PCP, {Fe(pz)[Pd(CN)4]} (pz=pyrazine), by the temperature dependence of Raman spectra. The ortho (o)-para (p) conversion process of H2 is forbidden for an isolated molecule. The charge density study using synchrotron radiation X-ray diffraction reveals the electric field generated in coordination nano-space. The present results corroborate similar findings observed on different systems and confirm that o-p conversion can occur on non-magnetic solids and that electric field can induce the catalytic hydrogen o-p conversion.

| S-EPMC4632575 | biostudies-literature

Rotational coherence of encapsulated ortho and para water in fullerene-C<sub>60</sub> revealed by time-domain terahertz spectroscopy.

Project description:We resolve the real-time coherent rotational motion of isolated water molecules encapsulated in fullerene-C60 cages by time-domain terahertz (THz) spectroscopy. We employ single-cycle THz pulses to excite the low-frequency rotational motion of water and measure the subsequent coherent emission of electromagnetic waves by water molecules. At temperatures below?~?100 K, C60 lattice vibrational damping is mitigated and the quantum dynamics of confined water are resolved with a markedly long rotational coherence, extended beyond 10 ps. The observed rotational transitions agree well with low-frequency rotational dynamics of single water molecules in the gas phase. However, some additional spectral features with their major contribution at?~2.26 THz are also observed which may indicate interaction between water rotation and the C60 lattice phonons. We also resolve the real-time change of the emission pattern of water after a sudden cooling to 4 K, signifying the conversion of ortho-water to para-water over the course of 10s hours. The observed long coherent rotational dynamics of isolated water molecules confined in C60 makes this system an attractive candidate for future quantum technology.

| S-EPMC7592058 | biostudies-literature

Quantum Rabi Model with Trapped Ions.

Project description:We propose the quantum simulation of the quantum Rabi model in all parameter regimes by means of detuned bichromatic sideband excitations of a single trapped ion. We show that current setups can reproduce, in particular, the ultrastrong and deep strong coupling regimes of such a paradigmatic light-matter interaction. Furthermore, associated with these extreme dipolar regimes, we study the controlled generation and detection of their entangled ground states by means of adiabatic methods. Ion traps have arguably performed the first quantum simulation of the Jaynes-Cummings model, a restricted regime of the quantum Rabi model where the rotating-wave approximation holds. We show that one can go beyond and experimentally investigate the quantum simulation of coupling regimes of the quantum Rabi model that are difficult to achieve with natural dipolar interactions.

| S-EPMC4611475 | biostudies-other

Comparative analysis of the toxicogenomic effects of Ortho-Benzyl-Para-ChloroPhenol (OBPCP) and Para-Tertiary AmylPhenol (PTAP) on Staphylococcus aureus

Project description:This SuperSeries is composed of the SubSeries listed below.

2013-01-01 | GSE40450 | GEO

Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions.

Project description:Diels-Alder cycloadditions are efficient routes for the synthesis of cyclic organic compounds. There has been a long-standing discussion whether these reactions proceed via stepwise or concerted mechanisms. Here, we adopt an experimental approach to explore the mechanism of the model polar cycloaddition of 2,3-dibromo-1,3-butadiene with propene ions by probing its conformational specificities in the entrance channel under single-collision conditions in the gas phase. Combining a conformationally controlled molecular beam with trapped ions, we find that both conformers of the diene, gauche and s-trans, are reactive with capture-limited reaction rates. Aided by quantum-chemical and quantum-capture calculations, this finding is rationalised by a simultaneous competition of concerted and stepwise reaction pathways, revealing an interesting mechanistic borderline case.

| S-EPMC8523519 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data