DFT Study of the NMR Properties of Xenon in Covalent Compounds and van der Waals Complexes—Implications for the Use of <sup>129</sup>Xe as a Molecular Probe

Bagno, Alessandro; Saielli, Giacomo

doi:10.1002/chem.200390168

Cited by 52 publications

(46 citation statements)

References 92 publications

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“…In this regard it is interesting to consider chemically unbound spin systems. In this case, a finite J coupling can still arise due to second-order hyperfine interaction in van der Waals molecules [47]. For example, in a mixture of liquid 129 Xe and pentane, a J coupling of 2.7 Hz was measured in agreement with predictions [48].…”

supporting

confidence: 60%

Constraints on Short-Range Spin-Dependent Interactions from Scalar Spin-Spin Coupling in Deuterated Molecular Hydrogen

2013

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A comparison between existing nuclear magnetic resonance measurements and calculations of the scalar spin-spin interaction (J-coupling) in deuterated molecular hydrogen (HD) yields stringent constraints on anomalous spin-dependent potentials between nucleons at the atomic scale (∼ 1Å). The dimensionless coupling constant g p P g N P /4π associated with exchange of pseudoscalar (axion-like) bosons between nucleons is constrained to be less than 5 × 10 −7 for boson masses in the range of 5 keV, representing improvement by a factor of 100 over previous constraints. The dimensionless coupling constant g −19 for bosons of mass < ∼ 1000 eV, improving constraints at this distance scale by a factor of 100 for proton-proton couplings and more than 8 orders of magnitude for neutron-proton couplings.PACS numbers: 14.80. Va, 11.40.Ha, Over the past few decades, searches for anomalous spin-dependent forces have drawn considerable interest as a signature of the axion [1], a hypothetical pseudoscalar Goldstone boson [2,3] arising out of the Peccei-Quinn solution to the strong-CP problem [4,5]. Axions are also appealing as a candidate for dark matter [6]. Other exotic spin-dependent interactions are predicted by a variety of novel theories such as those involving para-photons [7] and unparticles [8].The possible spin-dependent forces that could arise from exchange of scalar/pseudoscalar or vector gauge bosons are enumerated in Ref. [9]. Another theoretical framework for considering anomalous spin-dependent interactions comes from introducing nonzero torsion into general relativity, which causes gravity to acquire scalar and vector components that manifest as new spin-mass and spin-spin couplings [10][11][12][13]. Spontaneous Lorentz violation may also generate exotic spindependent interactions [14].Recent experiments have significantly improved constraints on long-range (tens of cm) dipole-dipole interactions between neutrons [15, 16] and monopole-dipole interactions between electrons and nucleons [17]. Earlier work constrained monopole-dipole interactions between nuclei [18] and anomalous dipole-dipole interactions between electrons [19,20] and electrons and nuclei [21]. Constraints on new pseudoscalar interactions can also be obtained from spin-independent tests of the inverse square law [22]. Other laboratory experiments constrain anomalous monopole-dipole couplings on length scales in the range of µm to mm [23][24][25][26]. Spin relaxation studies of hyperpolarized 3 He gas have been used to limit anomalous dipole-dipole interactions between neutrons at length scales of about 100 nm [27]. Because of the possibility that new force-mediating bosons may be massive and have limited range, it is of considerable interest to find experimental techniques to search for anomalous spin-dependent interactions at even shorter distances.Here we discuss constraints on the existence of anomalous dipole-dipole forces on angstrom length scales. Our constraints are obtained by comparison of nuclear magnetic resonance (NMR) measurements and th...

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supporting

confidence: 60%

Constraints on Short-Range Spin-Dependent Interactions from Scalar Spin-Spin Coupling in Deuterated Molecular Hydrogen

2013

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“…Reference 13 reported a comparison of CCSD and B3LYP results for intermolecular couplings, with the latter level consistently providing the correct sign and order of magnitude. The present relative magnitudes of the different NR contributions resemble the findings of Bagno and Saielli 9 and Pecul et al 12 in that, besides the dominating contact term, also the orbital contribution (PSO) is of importance, and the spindipole term is unimportant.…”

Section: Resultssupporting

confidence: 88%

“…(10) by r max → ∞, the average coupling constant decays to zero as the inverse of the number of atoms N. This can be seen from Eq. (9), where the denominator scales as O(N 2 ) whereas the numerator increases only linearly with N due to the finite spatial extent of the function J(r). Figure 3(b) reveals that contributions to the average coupling are only obtained from Xe-Xe pairs that have the internuclear separation within the range 3.5-5.5 Å.…”

Section: Spin-spin Coupling In Liquid Xenonmentioning

confidence: 99%

Nuclear spin-spin coupling in a van der Waals-bonded system: Xenon dimer

Vaara

Hanni

Jokisaari

2013

The Journal of Chemical Physics

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Nuclear spin-spin coupling over van der Waals bond has recently been observed via the frequency shift of solute protons in a solution containing optically hyperpolarized 129 Xe nuclei. We carry out a first-principles computational study of the prototypic van der Waals-bonded xenon dimer, where the spin-spin coupling between two magnetically non-equivalent isotopes, J( 129 Xe − 131 Xe), is observable. We use relativistic theory at the four-component Dirac-Hartree-Fock and Diracdensity-functional theory levels using novel completeness-optimized Gaussian basis sets and choosing the functional based on a comparison with correlated ab initio methods at the nonrelativistic level. J-coupling curves are provided at different levels of theory as functions of the internuclear distance in the xenon dimer, demonstrating cross-coupling effects between relativity and electron correlation for this property. Calculations on small Xe clusters are used to estimate the importance of many-atom effects on J( 129 Xe − 131 Xe). Possibilities of observing J( 129 Xe − 131 Xe) in liquid xenon are critically examined, based on molecular dynamics simulation. A simplistic spherical model is set up for the xenon dimer confined in a cavity, such as in microporous materials. It is shown that the on the average shorter internuclear distance enforced by the confinement increases the magnitude of the coupling as compared to the bulk liquid case, rendering J( 129 Xe − 131 Xe) in a cavity a feasible target for experimental investigation.

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“…This shows that relatively high binding energies do not necessarily mean large chemical shifts for xenon. The interaction of xenon with single halogen ions can however lead to enormous shifts like 47,00 ppm for Cl ϩ (33).…”

mentioning

confidence: 99%

¹²⁹Xe on Ir(111): NMR study of xenon on a metal single crystal surface

Jänsch

Gerhard

Koch

2004

Proc. Natl. Acad. Sci. U.S.A.

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NMR experiments of 129 Xe adsorbed on an iridium single crystal surface are reported. Very high nuclear polarization (P z Ϸ 0.7) makes the experiment possible. A coverage of less then one monolayer is investigated on the Ir(111) surface with an area of 0.8 cm 2 . The observed resonance line shifts are very large and highly anisotropic. We find iso ‫؍‬ 1,032 ؎ 11 ppm and an ‫؍‬ 291 ؎ 33 ppm, which are far above the typical range of physisorption. The highly ordered substrate leads to homogeneous conditions for the xenon atoms, as seen in the narrow linewidth of 20 ppm. Chemical shifts under physisorption conditions are not large enough to totally explain the results. Knight shift can clearly be identified as the cause of the findings. This shift shows the presence of conduction electrons of the metallic substrate at the xenon nucleus and thus the mixing of metallic and atomic states at the Fermi level. Such mixing is in accordance with recent Hartree-Fock and density functional calculations of similar van der Waals adsorption systems. Quantitative comparisons, however, fail completely. The size and ratio of an and iso are pure ground-state properties in a structurally simple system. They are accessible to theory and provide detailed local information that can serve as a benchmark for theory.

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DFT Study of the NMR Properties of Xenon in Covalent Compounds and van der Waals Complexes—Implications for the Use of ¹²⁹Xe as a Molecular Probe

Cited by 52 publications

References 92 publications

Constraints on Short-Range Spin-Dependent Interactions from Scalar Spin-Spin Coupling in Deuterated Molecular Hydrogen

Constraints on Short-Range Spin-Dependent Interactions from Scalar Spin-Spin Coupling in Deuterated Molecular Hydrogen

Nuclear spin-spin coupling in a van der Waals-bonded system: Xenon dimer

¹²⁹Xe on Ir(111): NMR study of xenon on a metal single crystal surface

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DFT Study of the NMR Properties of Xenon in Covalent Compounds and van der Waals Complexes—Implications for the Use of 129Xe as a Molecular Probe

Cited by 52 publications

References 92 publications

Constraints on Short-Range Spin-Dependent Interactions from Scalar Spin-Spin Coupling in Deuterated Molecular Hydrogen

Constraints on Short-Range Spin-Dependent Interactions from Scalar Spin-Spin Coupling in Deuterated Molecular Hydrogen

Nuclear spin-spin coupling in a van der Waals-bonded system: Xenon dimer

129Xe on Ir(111): NMR study of xenon on a metal single crystal surface

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DFT Study of the NMR Properties of Xenon in Covalent Compounds and van der Waals Complexes—Implications for the Use of ¹²⁹Xe as a Molecular Probe

¹²⁹Xe on Ir(111): NMR study of xenon on a metal single crystal surface