Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters

Weijo, Ville; Bast, Radovan; Manninen, Pekka; Saue, Trond; Vaara, Juha

doi:10.1063/1.2436886

Cited by 22 publications

(25 citation statements)

References 42 publications

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“…Other proposed experiments include measurement of frequency splittings in nuclear magnetic resonance (NMR), EPR, microwave (MW) and Mössbauer spectroscopy. Alternative approaches aim for instance at a measurement of time‐dependence in optical activity or at the direct detection of the absolute value of the parity violating energy difference in the electronic ground state or electronically excited states .…”

Section: …For Chiral Molecules?mentioning

confidence: 99%

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Parity violation

Berger

Stohner

2019

WIREs Comput Mol Sci

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Violation of (space) parity in atomic physics, molecular physics and chemistry is briefly reviewed. The review is structured by frequently asked questions related to the concept of space parity, its violation and the consequences thereof in physics, chemistry and biology. This article is categorized under: Theoretical and Physical Chemistry > Spectroscopy Structure and Mechanism > Molecular Structures Theoretical and Physical Chemistry > Thermochemistry K E Y W O R D S chirality, electroweak quantum chemistry, fundamental symmetries, parity violation, periodic system of fundamental particles, relativistic quantum chemistry 1 | WHAT IS (SPACE) PARITY?In mathematics, the concept of even and odd parity is related to integer numbers and their behavior under division by the number two. Those integers which can be divided by two without remainder are called even, those that are divided by two with remainder one are called odd. Consequently, one can speak of a given integer to possess either even parity or odd parity (see also Reference 1). In quantum mechanics, instead, the term parity is used for the transformation properties of states and operators with respect to discrete symmetry operations such as space inversion, time reversal or charge conjugation. Space inversion (in conventional three-dimensional space) implies reflection of spatial coordinates of all particles at the origin, time reversal implies reversal of all particle momenta and charge conjugation implies change from particles to their anti-particles and vice versa. States that remain unaltered under application of such a discrete symmetry operation are called space parity even (Peven) or charge parity even (C-even), respectively, those which change sign under application of these discrete symmetry operations are called space parity odd (P-odd) or charge parity odd (C-odd). Time reversal is special in this regard as the corresponding operator describing time reversal is an antiunitary operator which does not have eigenvalues. In contrast to states, operators can be classified as being time parity even (T-even) or time parity odd (T-odd) (see Reference 2 for a more detailed discussion of time-reversal symmetry). When no additional classification is given, the word parity conventionally refers to space parity, and we will use that convention also within this review.An arbitrary quantum state does not necessarily have to possess well-defined parity (P-even or P-odd), but in linear quantum mechanics instead, such a quantum state can be written as a superposition of states with well-defined parity.Elementary particles as quanta of fields are usually described with the help of so-called intrinsic parities (see e.g., Reference 3). One characterizes these fields for instance as scalar fields and vector fields or pseudo-scalar fields and pseudo-scalar fields and vector fields, depending on their behavior with respect to space inversion. Scalar fields and pseudo-vector fields remain

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Section: …For Chiral Molecules?mentioning

confidence: 99%

“…A different numerical route is required to predict parity violating effects in NMR spectra of chiral compounds . For this purpose, linear and nonlinear response theoretical approaches are employed to compute parity violating contributions to NMR shielding tensors and indirect spin–spin coupling constants.…”

Section: …For Chiral Molecules?mentioning

confidence: 99%

Parity violation

Berger

Stohner

2019

WIREs Comput Mol Sci

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“…I varies significantly near the equilibrium geometry as a function of the dihedral angle. 20,22,64,65 This compound has a torsional mode around the OO bond, giving rise to a double minimum potential. The property of interest may depend on nuclear geometry, and it needs to be averaged over the vibrational ground state, giving rise to the zero-point vibrational averages (ZPVA) correction.…”

Section: Chf-(i) Chf-(v)mentioning

confidence: 99%

Electric field effects on nuclear magnetic shielding of the 1:1 and 2:1 (homo and heterochiral) complexes of XOOX′ (X, X′ = H, CH3) with lithium cation and their chiral discrimination

Alkorta

Elguero

Provasi

et al. 2011

The Journal of Chemical Physics

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The set of 1:1 and 2:1 complexes of XOOX' (X, X' = H, CH(3)) with lithium cation has been studied to determine if they are suitable candidates for chiral discrimination in an isotropic medium via nuclear magnetic resonance spectroscopy. Conventional nuclear magnetic resonance is unable to distinguish between enantiomers in the absence of a chiral solvent. The criterion for experimental detection is valuated by the isotropic part of nuclear shielding polarisability tensors, related to a pseudoscalar of opposite sign for two enantiomers. The study includes calculations at coupled Hartree-Fock and density functional theory schemes for (17)O nucleus in each compound. Additional calculations for (1)H are also included for some compounds. A huge static homogeneous electric field, perpendicular to the magnetic field of the spectromer, as big as ≈1.7 × 10(8) V m(-1) should be applied to observe a shift of ≈1 ppm for (17)O magnetic shielding in the proposed set of complexes.

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“…Laubender and Berger found that PV in NMR shielding constants for the heavy elements in H 2 O 2 , H 2 S 2 , and H 2 Se 2 computed at the CCSD level of theory deviate from their uncorrelated counterparts typically by approximately 20%, with varying more pronounced corrections at the equilibrium structures, while in 2-fluorooxirane, electron correlation changes the shielding constants by almost 100% [168]. For the same H 2 X 2 molecules at their equilibrium structures, Weijo et al found that coupled-cluster and DFT results for PV contributions differ significantly from the HF data, that is, for the 77 Se PV shift in the nuclear shielding constant for H 2 Se 2 , they obtain (in 10 À10 ppm) 256.1 (HF), 139.9 (CCSD), 116.8 (B3LYP), 60.5 (BP86), 128.6 (PBE0), and 68.6 (PBE) [173]. Similarly, for the PV contribution to the Se-Se spin-spin coupling, they calculate (in nHz) À6.606 (HF), À3.181 (CCSD), À3.038 (B3LYP), À1.943 (BP86), À3.795 (PBE0), and À2.081 (PBE).…”

Section: Theoretical Predictionsmentioning

confidence: 99%

“…Similarly, for the PV contribution to the Se-Se spin-spin coupling, they calculate (in nHz) À6.606 (HF), À3.181 (CCSD), À3.038 (B3LYP), À1.943 (BP86), À3.795 (PBE0), and À2.081 (PBE). They also showed that basis set effects are very pronounced, especially at the correlated level of theory, and that the choice of the nuclear charge distribution model (point charge or extended Gaussian) has a significant impact on the PV contribution in the spin-spin coupling constant [173]. Vibrational effects in parity-violating contributions to the isotropic nuclear magnetic resonance chemical shift were recently investigated for CHFClBr by Weijo et al [174].…”

Section: Theoretical Predictionsmentioning

confidence: 99%

The Search for Parity Violation in Chiral Molecules

Schwerdtfeger

2010

Computational Spectroscopy

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Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters

Cited by 22 publications

References 42 publications

Parity violation

Parity violation

Electric field effects on nuclear magnetic shielding of the 1:1 and 2:1 (homo and heterochiral) complexes of XOOX′ (X, X′ = H, CH3) with lithium cation and their chiral discrimination

The Search for Parity Violation in Chiral Molecules

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