Nuclear spin optical rotation and Faraday effect in gaseous and liquid water

Pennanen, Teemu S.; Ikäläinen, Suvi; Lantto, Perttu; Vaara, Juha

doi:10.1063/1.4711957

Cited by 24 publications

(75 citation statements)

References 40 publications

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“…10 This phenomenon was predicted using firsta) juha.vaara@iki.fi b) coriani@units.it principles calculations according to the response theory formulation of the underlying antisymmetric polarizability. 6 Further experimental [11][12][13] and theoretical [14][15][16] work has been reported for NSOR. Nuclear spin-and electric quadrupole moment-induced Cotton-Mouton effects have been theoretically investigated in Refs.…”

Section: Introductionmentioning

confidence: 99%

“…The antisymmetric polarizability underlying NSOR increases rapidly as the incident light frequency approaches optical excitations, [23][24][25] which has been proposed to facilitate a means of gaining chemical resolution of the nuclear magneto-optic rotation signals arising from the different chromophores of the molecule. 6 The first-principles NSOR calculations carried out so far 6,10,15,16 have all been performed with conventional quadratic response theory, 26 disregarding the fact that the perturbational approach is not valid in the vicinity of the excitation energies. Hence, it remains a question whether the conclusions drawn in the earlier work remain valid in a more realistic treatment of the near-resonant spectral regions.…”

Section: Introductionmentioning

confidence: 99%

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Nuclear spin circular dichroism

Vaara¹,

Rizzo²,

Kauczor³

et al. 2014

The Journal of Chemical Physics

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Articles you may be interested inMagnetic circular dichroism of symmetry and spin forbidden transitions of high-spin metal ions J. Chem. Phys. 113, 5003 (2000) Recent years have witnessed a growing interest in magneto-optic spectroscopy techniques that use nuclear magnetization as the source of the magnetic field. Here we present a formulation of magnetic circular dichroism (CD) due to magnetically polarized nuclei, nuclear spin-induced CD (NSCD), in molecules. The NSCD ellipticity and nuclear spin-induced optical rotation (NSOR) angle correspond to the real and imaginary parts, respectively, of (complex) quadratic response functions involving the dynamic second-order interaction of the electron system with the linearly polarized light beam, as well as the static magnetic hyperfine interaction. Using the complex polarization propagator framework, NSCD and NSOR signals are obtained at frequencies in the vicinity of optical excitations. Hartree-Fock and density-functional theory calculations on relatively small model systems, ethene, benzene, and 1,4-benzoquinone, demonstrate the feasibility of the method for obtaining relatively strong nuclear spin-induced ellipticity and optical rotation signals. Comparison of the proton and carbon-13 signals of ethanol reveals that these resonant phenomena facilitate chemical resolution between non-equivalent nuclei in magneto-optic spectra. © 2014 AIP Publishing LLC.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nuclear spin circular dichroism

Vaara¹,

Rizzo²,

Kauczor³

et al. 2014

The Journal of Chemical Physics

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“…For the larger molecules, the experimental values are reproduced qualitatively. A detailed analysis would necessitate the incorporation of solvation and intramolecular dynamics effects via molecular dynamics simulations [32]. In the case of perfluorohexane, the known issues [29] of the present DFT functionals with the hyperfine properties of 19 F may contribute to the observed overestimation.…”

mentioning

confidence: 99%

“…This is due to the involvement of both the magnetic hyperfine and electric dipole operators. The efficiency of co sets for magnetic properties has been verified in several studies [5,22,[30][31][32]. The co-2 set (10s7p3d primitive functions for C-O; 10s7p3d for H) was developed in Ref.…”

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confidence: 99%

“…Co-0 (C-O: 12s10p4d1f , H: 8s8p5d) was generated in Ref. [32] for basis-set-converged NSOR for first-row main-group systems, as calibrated by 1 H and 19 FSOR calculations for the FH molecule. To assess V B , the Verdet constants were calculated at the BHandHLYP/co-2 and B3LYP/co-2 levels for all molecules, as well as at the CCSD/co-2 level for water, methanol, ethanol, propanol, and isopropanol [13].…”

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confidence: 99%

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Observation of Optical Chemical Shift by Precision Nuclear Spin Optical Rotation Measurements and Calculations

Shi¹,

Ikäläinen

Vaara

et al. 2013

J. Phys. Chem. Lett.

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*Nuclear spin optical rotation (NSOR) is a recently developed technique for detection of nuclear magnetic resonance via rotation of light polarization, instead of the usual long-range magnetic fields. NSOR signals depend on hyperfine interactions with virtual optical excitations, giving new information about the nuclear chemical environment. We use a multi-pass optical cell to perform first precision measurements of NSOR signals for a range of organic liquids and find clear distinction between proton signals for different compounds, in agreement with our earlier predictions. Detailed first principles quantum-mechanical NSOR calculations are found to be in good agreement with the measurements. The effect of light on nuclear magnetic resonance (NMR) has been the subject of considerable interest, as it can be used to further increase the power of NMR spectroscopy [1,2]. While NMR frequency shifts due to laser light turned out to be too small to be easily measured [3], the inverse effect of optical rotation (OR) caused by nuclear spin polarization was observed in water and liquid 129 Xe [4]. The rotation of light polarization is similar to the Faraday effect caused by nuclear magnetization, but is enhanced by the hyperfine interaction between nuclear spins and virtual electronic excitations. Recent firstprinciples calculations of the nuclear spin OR (NSOR) predict different signals from chemically non-equivalent nuclei, opening the possibility of a new chemical analysis technique combining optical and NMR spectroscopy [5]. However, the signal-to-noise ratio (SNR) of NSOR detection has been poor in the first experiments utilizing low-field CW NMR [4] and in high-field pulsed experiments [6,7]. NSOR differences between the same nuclei in different molecular positions have not been clearly observed [7].Here we use a multi-pass optical cell [8,9] to measure proton NSOR with an SNR greater than 15 after 1000 seconds of integration and perform systematic NSOR measurements on organic liquids with absolute uncertainty of 5%. Contrary to recent report [7], we find that the NSOR signals do not scale with the Verdet constant V of the liquid since the hyperfine interaction between electrons and nuclei is influenced by the chemical environment. The ratio of NSOR to Faraday rotation and to inductive 1 H signals ranges by more than a factor of 2 for the simple chemicals studied. We also apply the recent first-principles theoretical method [5] for calculation of NSOR and obtain results in good qualitative agreement with our measurements for both 1 H and 19 F spins.

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Nuclear‐Spin‐Induced Cotton–Mouton Effect in a Strong External Magnetic Field

Vaara

2014

ChemPhysChem

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Novel, high-sensitivity and high-resolution spectroscopic methods can provide site-specific nuclear information by exploiting nuclear magneto-optic properties. We present a first-principles electronic structure formulation of the recently proposed nuclear-spin-induced Cotton-Mouton effect in a strong external magnetic field (NSCM-B). In NSCM-B, ellipticity is induced in a linearly polarized light beam, which can be attributed to both the dependence of the symmetric dynamic polarizability on the external magnetic field and the nuclear magnetic moment, as well as the temperature-dependent partial alignment of the molecules due to the magnetic fields. Quantum-chemical calculations of NSCM-B were conducted for a series of molecular liquids. The overall order of magnitude of the induced ellipticities is predicted to be 10(-11) -10(-6) rad T(-1) M(-1) cm(-1) for fully spin-polarized nuclei. In particular, liquid-state heavy-atom systems should be promising for experiments in the Voigt setup.

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Nuclear spin optical rotation and Faraday effect in gaseous and liquid water

Cited by 24 publications

References 40 publications

Nuclear spin circular dichroism

Nuclear spin circular dichroism

Observation of Optical Chemical Shift by Precision Nuclear Spin Optical Rotation Measurements and Calculations

Nuclear‐Spin‐Induced Cotton–Mouton Effect in a Strong External Magnetic Field

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