Gas-phase Nuclear Magnetic Resonance Research Articles

Preparation of ultracold ions in strong magnetic field and application to gas-phase NMR spectroscopy II

This paper presents a gas-phase nuclear magnetic resonance (NMR) apparatus, which may enable a tandem combination with an ion cyclotron resonance mass spectrometer. The NMR technique is widely used for analyzing the physical and chemical properties of materials; however, it is mostly limited to materials in condensed phases. Here, we construct a gas-phase NMR apparatus to extend this technique to gas-phase molecular ions. We outline the principle of NMR detection based on a Stern-Gerlach-type experiment and describe the experimental procedures and results for the preparation and manipulation of ultracold ions, which are fundamental for the proposed NMR detection. The development of the gas-phase NMR probe and radio-frequency excitation system and the features of the apparatus are presented. We also discuss the feasibility of combining this apparatus with an ion cyclotron resonance cell for realizing an NMR apparatus for mass-selected molecular ions briefly.

Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies.

The heterogeneous solid-gas reactions of crystals of [Rh(L2)(propene)][BArF4] (1, L2 = tBu2PCH2CH2PtBu2) with H2 and propene, 1-butene, propyne, or 1-butyne are explored by gas-phase nuclear magnetic resonance (NMR) spectroscopy under batch conditions at 25 °C. The temporal evolution of the resulting parahydrogen-induced polarization (PHIP) effects measures catalytic flux and thus interrogates the efficiency of catalytic pairwise para-H2 transfer, speciation changes in the crystalline catalyst at the molecular level, and allows for high-quality single-scan 1H, 13C NMR gas-phase spectra for the products to be obtained, as well as 2D-measurements. Complex 1 reacts with H2 to form dimeric [Rh(L2)(H)(μ-H)]2[BArF4]2 (4), as probed using EXAFS; meanwhile, a single-crystal of 1 equilibrates NMR silent para-H2 with its NMR active ortho isomer, contemporaneously converting into 4, and 1 and 4 each convert para-H2 into ortho-H2 at different rates. Hydrogenation of propene using 1 and para-H2 results in very high initial polarization levels in propane (>85%). Strong PHIP was also detected in the hydrogenation products of 1-butene, propyne, and 1-butyne. With propyne, a competing cyclotrimerization deactivation process occurs to afford [Rh(tBu2PCH2CH2PtBu2)(1,3,4-Me3C6H3)][BArF4], while with 1-butyne, rapid isomerization of 1-butyne occurs to give a butadiene complex, which then reacts with H2 more slowly to form catalytically active 4. Surprisingly, the high PHIP hydrogenation efficiencies allow hyperpolarization effects to be seen when H2 is taken directly from a regular cylinder at 25 °C. Finally, changing the chelating phosphine to Cy2PCH2CH2PCy2 results in initial high polarization efficiencies for propene hydrogenation, but rapid quenching of the catalyst competes to form the zwitterion [Rh(Cy2PCH2CH2PCy2){η6-(CF3)2(C6H3)}BArF3].

Isotope Effects on Nuclear Magnetic Shielding in Molecular Hydrogen.

The secondary isotope shifts of six molecular hydrogen isotopologues (H2, D2, T2, HD, HT, and DT) were measured using gas-phase nuclear magnetic resonance spectroscopy. It was found that these isotope shifts are in satisfying agreement with performed ab initio quantum chemistry computations. However, there is a small systematic discrepancy between results of experiments and computations, i.e., the magnitudes of computed shifts are approximately 10% larger than those obtained from the experiments. This indicates that computations performed using the Born-Oppenheimer approximation are not sufficient for reproducing quantitatively the experimentally determined secondary isotope shifts of molecular hydrogen.

Gas-phase nuclear magnetic resonance study of internal isomerization in perfluoro-2-azapropene: Comparison of experimental and computed kinetic parameters

Rate constants obtained from total line-shape analysis of five temperature-dependent gas-phase NMR spectra of perfluoroazapropene yielded the kinetic barrier to internal isomerization: G‡298 = 66.9 (0.4) kJ mol−1. Five temperature-dependent liquid spectra (5 mol% in CDCl3) yielded G‡298 = 67.4 (0.8) kJ mol−1. Ab initio calculations performed using the compound methods Complete Basis Set (CBS-4M, QB3, APNO), Gaussian (G1-4), and Weizmann (W1U, WBD) gave results consistent with a transition state corresponding to nitrogen inversion. The values that best matched the experimental G‡298 value for each compound method were 63.9 kJ mol−1 (CBS-APNO), 66.1 kJ mol−1 (G2), and 65.6 kJ mol−1 (W1BD).

Indirect Spin-Spin Coupling Constants in the Hydrogen Isotopologues.

The results of experimental and theoretical studies of indirect spin-spin coupling constants for hydrogen deuteride (HD), hydrogen tritide (HT), and deuterium tritide (DT) are described. The reduced coupling constants obtained from the gas-phase NMR (nuclear magnetic resonance) experiment conducted at 300 K are 2.338(1), 2.334(3), and 2.316(1) × 10(20) T(2) J(-1), while the ab initio values computed at the full configuration interaction level of theory equal 2.349(3), 2.343(3), and 2.322(3) × 10(20) T(2) J(-1) for HD, HT, and DT, respectively. The agreement of the experimental and theoretical results is improved when proper treatment of the influence of nuclear relaxation on the NMR spectrum is applied. However, there is a minor discrepancy between experiment and theory, exceeding the estimated error bars; potential sources of this discrepancy are discussed.

NMR absolute shielding scale and nuclear magnetic dipole moment of (207)Pb.

An absolute shielding scale is proposed for (207)Pb nuclear magnetic resonance (NMR) spectroscopy. It is based on ab initio calculations performed on an isolated tetramethyllead Pb(CH3)4 molecule and the assignment of the experimental resonance frequency from the gas-phase NMR spectra of Pb(CH3)4, extrapolated to zero density of the buffer gas to obtain the result for an isolated molecule. The computed (207)Pb shielding constant is 10 790 ppm for the isolated molecule, leading to a shielding of 10799.7 ppm for liquid Pb(CH3)4 which is the accepted reference standard for (207)Pb NMR spectra. The new experimental and theoretical data are used to determine μ((207)Pb), the nuclear magnetic dipole moment of (207)Pb, by applying the standard relationship between NMR frequencies, shielding constants and nuclear moments of two nuclei in the same external magnetic field. Using the gas-phase (207)Pb and (reference) proton results and the theoretical value of the Pb shielding in Pb(CH3)4, we find μ((207)Pb) = 0.59064 μN. The analysis of new experimental and theoretical data obtained for the Pb(2+) ion in water solutions provides similar values of μ((207)Pb), in the range of 0.59000-0.59131 μN.

Organometallic Ruthenium Nanoparticles as Model Catalysts for CO Hydrogenation: A Nuclear Magnetic Resonance and Ambient-Pressure X-ray Photoelectron Spectroscopy Study

We present a study of the structure and reactivity of Ru nanoparticles of different sizes (1.3, 1.9, and 3.1 nm) for CO hydrogenation using gas-phase nuclear magnetic resonance and mass spectroscopy. In addition, the nanoparticles were characterized under reaction mixtures in situ by ambient-pressure X-ray photoelectron spectroscopy. We found that during reaction the Ru is in the metallic state and that the diphosphine ligands [bis(diphenylphosphino)butane (dppb)] on the surface of 1.9 and 3.1 nm nanoparticles not only act as capping and protecting agents but also stay on the surface during reaction and improve their activity and selectivity toward C2–C4 hydrocarbons.

NMR Shielding Constants in PH3, Absolute Shielding Scale, and the Nuclear Magnetic Moment of 31P

Ab initio values of the absolute shielding constants of phosphorus and hydrogen in PH(3) were determined, and their accuracy is discussed. In particular, we analyzed the relativistic corrections to nuclear magnetic resonance (NMR) shielding constants, comparing the constants computed using the four-component Dirac-Hartree-Fock approach, the four-component density functional theory (DFT), and the Breit-Pauli perturbation theory (BPPT) with nonrelativistic Hartree-Fock or DFT reference functions. For the equilibrium geometry, we obtained σ(P) = 624.309 ppm and σ(H) = 29.761 ppm. Resonance frequencies of both nuclei were measured in gas-phase NMR experiments, and the results were extrapolated to zero density to provide the frequency ratio for an isolated PH(3) molecule. This ratio, together with the computed shielding constants, was used to determine a new value of the nuclear magnetic dipole moment of (31)P: μ(P) = 1.1309246(50) μ(N).

Weak intermolecular interactions in gas-phase nuclear magnetic resonance

Gas-phase nuclear magnetic resonance (NMR) spectra demonstrating the effect of weak intermolecular forces on the NMR shielding constants of the interacting species are reported. We analyse the interaction of the molecular hydrogen isotopomers with He, Ne, and Ar, and the interaction in the He-CO(2) dimer. The same effects are studied for all these systems in the ab initio calculations. The comparison of the experimental and computed shielding constants is shown to depend strongly on the treatment of the bulk susceptibility effects, which determine in practice the pressure dependence of the experimental values. Best agreement of the results is obtained when the bulk susceptibility correction in rare gas solvents is evaluated from the analysis of the He-rare gas interactions, and when the shielding of deuterium in D(2)-rare gas systems is considered.

An Apparatus for Production of Isotopically and Spin-Enriched Hydrogen for Induced Polarization Studies

An apparatus for the production of hydrogen for hydrogenation-induced polarization studies was developed. The apparatus provides hydrogen gas from a solid source, thereby simplifying the requirement for siting of the apparatus. The produced hydrogen can be either isotopically enriched (with deuterium) or spin-enriched (with parahydrogen). These specialty gases were produced at small predetermined quantities and ambient pressure. The properties of the hydrogen mixtures were characterized by gas-phase nuclear magnetic resonance. The T 1 of the hydrogen mixtures (3.7 ms) was not affected by para-enrichment. The line width of the hydrogen signal in the para-enriched mixture was 34% larger. The reaction of ethyl propiolate hydrogenation served to evaluate the performance in terms of the ability to create hyperpolarized states. In this reaction, a polarization of 11.2% was measured for protons. Consecutive alkene hydrogenations as well as hydrogenations of the catalyst ligand resulted in additional hyperpolarized signals which were systematically assigned.

Gas-phase NMR technique for studying the thermolysis of materials: thermal decomposition of ammonium perfluorooctanoate.

The kinetics of the thermal decomposition of ammonium perfluorooctanoate (APFO) has been studied by high-temperature gas-phase nuclear magnetic resonance spectroscopy over the temperature range 196-234 degrees C. We find that APFO cleanly decomposes by first-order kinetics to give the hydrofluorocarbon 1-H-perfluoroheptane and is completely decomposed (>99%) in a matter of minutes at the upper limit of this temperature range. Based on the temperature dependence of the measured rate constants, we find that the enthalpy and entropy of activation are DeltaH++ = 150 +/- 11 kJ mol(-1) and DeltaS++ = 3 +/- 23 J mol(-)(1) deg(-1). These activation parameters may be used to calculate the rate of APFO decomposition at the elevated temperatures (350-400 degrees C) at which fluoropolymers are processed; for example, at 350 degrees C the half-life for APFO is estimated to be less than 0.2 s. Our studies provide the fundamental parameters involved in the decomposition of the ammonium salt of perfluorooctanoic acid and indicate the utility of gas-phase NMR for thermolysis studies of a variety of materials that release compounds that are volatile at the temperature of decomposition and that contain an NMR-active nucleus.

Physicochemical Properties of 8-2 Fluorinated Telomer B Alcohol

Physicochemical properties (vapor pressure, water solubility, gas-phase nuclear magnetic resonance) of 8-2 Telomer B alcohol, CF3(CF2)7CH2CH2OH, were measured. Vapor pressures were measured in the temperature range from (21 to 200) °C by three different methods, including a novel method based on gas-phase NMR that requires only milligram quantities of substance. At 21 °C, the vapor pressure was 3 Pa; at 201.3 °C, the vapor pressure was 101.325 kPa (1 atm). Water solubility was measured at (12, 25, 37, and 60) °C in pure water. Solubility ranged from (134 to 318) μg/L.

Shielding and spin-spin coupling constants from gas-phase NMR

Intermolecular interactions modify nuclear magnetic resonance (NMR) chemical shifts and spin-spin coupling constants. The intermolecular effects can be determined if the NMR parameters for an isolated molecule are known. Gas-phase NMR spectroscopy offers such methods which allow one to measure the shielding and spin-spin coupling constants at the zero-density limit where the NMR parameters are free from intermolecular contributions. It is also shown that at present the multinuclear NMR spectra can easily be obtained for gaseous samples containing several micrograms of a solute compound.

Pure- and Mixed-Gas Sorption Measurements on Zeolitic Adsorbents via Gas-Phase Nuclear Magnetic Resonance

Gas-phase NMR spectroscopy has been applied successfully in measuring pure- and mixed-gas equilibria on a 5A adsorbent for carbon monoxide, methane, and nitrogen. The reliability of the technique is established by comparing data collected in this paper to pure-gas isotherms measured at 23°C by standard volumetric expansion techniques in the pressure range of 0.5-5 atm. Mixed-gas equilibria data for binary gas mixtures as well as the ternary gas mixture are compared with predictions based on heterogeneous ideal solution adsorption theory analysis.

Novel MRI applications of laser-polarized noble gases

Gas-phase nuclear magnetic resonance (NMR) has great potential as a probe for a variety of interesting physical and biomedical problems that are not amenable to study by water or similar liquid. However, NMR of gases was largely neglected due to the low signal obtained from the thermally polarized gases with very low sample density. The advent of optical pumping techniques for enhancing the polarization of the noble gases3He and129Xe has bought new life to this field, especially in medical imaging where3He lung inhalation imaging is approaching a clinical application. However, there are numerous applications in materials science that also benefit from the use of these gases. We review primarily nonmedical applications of laser-polarized noble gases for both NMR imaging and spectroscopy and highlight progress with examples from our laboratory including high-resolution imaging at millitesla applied field strength and velocity imaging of convective flow. Porous media microstucture has been probed with both thermal and laser-polarized xenon, as xenon is an ideal probe due to low surface interaction with the grains of the porous media.

A magnetic resonance study of non-adiabatic evolution of spin quantum states

We use a nuclear-spin gyroscope for demonstrating non-adiabatic rotational effects and the geometric phase of a polarized Xe nuclear-spin ensemble. We treat a spin-1/2 model system in a rotating magnetic field (with its inherent single-valued eigenstates) and a spin-3/2 system in a rotating electric field gradient (with a partially degenerate eigenstate structure) including (i) spin polarization by polarization transfer from optically pumped alkali atoms, (ii) spin-coherence excitation, and (iii) detection. The results are compared to those obtained by the concept of geometric phases, where Berry's phase emerges as the adiabatic limit. Experimental results from gasphase nuclear magnetic resonance of129Xe (I=1/2) and131Xe (I=3/2) are in excellent agreement with theoretical predictions.

ChemInform Abstract: GAS‐PHASE NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF CHEMICAL EXCHANGE IN N,N‐DIMETHYLACETAMIDE. MEDIUM EFFECTS ON KINETIC PARAMETERS

Chemischer InformationsdienstVolume 15, Issue 39 Physical Organic Chemistry ChemInform Abstract: GAS-PHASE NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF CHEMICAL EXCHANGE IN N,N-DIMETHYLACETAMIDE. MEDIUM EFFECTS ON KINETIC PARAMETERS B. D. ROSS, B. D. ROSSSearch for more papers by this authorN. S. TRUE, N. S. TRUESearch for more papers by this authorG. B. MATSON, G. B. MATSONSearch for more papers by this author B. D. ROSS, B. D. ROSSSearch for more papers by this authorN. S. TRUE, N. S. TRUESearch for more papers by this authorG. B. MATSON, G. B. MATSONSearch for more papers by this author First published: September 25, 1984 https://doi.org/10.1002/chin.198439072Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume15, Issue39September 25, 1984 RelatedInformation

Gas-phase nuclear magnetic resonance investigation of chemical exchange in N,N-dimethylacetamide. Medium effects on kinetic parameters

Parametres cinetiques en phase gazeuse de la rotation interne dans le N,N-dimethylacetamide. Comparaison avec les resultats obtenus sur des echantillons liquides ou en solution

Inversion and tunneling in aziridine and aziridine-N-d. Gas-phase nuclear magnetic resonance band shape analysis and model calculations of the isotope effect

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTInversion and tunneling in aziridine and aziridine-N-d. Gas-phase nuclear magnetic resonance band shape analysis and model calculations of the isotope effectRobert E. Carter, Torbjorn Drakenberg, and Nils A. BergmanCite this: J. Am. Chem. Soc. 1975, 97, 24, 6990–6996Publication Date (Print):November 1, 1975Publication History Published online1 May 2002Published inissue 1 November 1975https://doi.org/10.1021/ja00857a008RIGHTS & PERMISSIONSArticle Views135Altmetric-Citations41LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (884 KB) Get e-Alerts Get e-Alerts