Parity-violating contributions to nuclear spin-rotation interactions and to NMR shielding constants in tetrahedral molecules

Aucar, I. Agustín; Chamorro, Yuly; Borschevsky, Anastasia

doi:10.1103/physreva.106.062802

Cited by 2 publications

(4 citation statements)

References 105 publications

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“…Furthermore, the method would be feasible to be applied for describing the PV contributions to EFG, as it was done for other properties. 16,17 After the description given by LRESC at the HF level, the next step of this study consists of including correlation effects at the DFT level of theory with several functionals for comparison with available theoretical and experimental results. This is done for Cl, Br, I, and At atoms.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The analysis given above shows that the LRESC scheme is capable of reproducing in a very precise way the EFG for chiral systems containing heavy atoms. Furthermore, the method would be feasible to be applied for describing the PV contributions to EFG, as it was done for other properties. , …”

Section: Resultsmentioning

confidence: 99%

“…14−16 There are also several works that emphasize the significant contribution of the electronic structure of the chiral center in enhancing PV effects, helping to understand which molecular structures are the best candidates toward experimental detection. 17,18 In 2020, Gaul and Berger 19 applied a quasi-relativistic twocomponent zero-order regular approximation (ZORA) to calculate the nuclear electric quadrupole coupling tensor of the chiral polyhalomethane derivatives CHFClBr and CHFClI. Such molecules have two nuclei with electric quadrupole moments, providing special challenges for the analysis of highresolution rovibrational spectra and making accurate calculations of nuclear quadrupole coupling parameters particularly valuable.…”

Section: ■ Introductionmentioning

confidence: 99%

“…It remains very challenging to detect this phenomenon, so numerous efforts have been made to find PV effects in molecules. , Several research projects have been proposed in recent years to investigate PV effects in molecules, with efforts focused on employing a variety of techniques, including rotational, vibrational, and electronic spectroscopy, to observe the frequency shifts caused by these effects. , Despite the increasing precision of the developed strategies, PV effects remain undetected, as tiny values are predicted theoretically. Another experimental strategy employed to attempt the observation of PV effects in chiral molecules involves the study of nuclear magnetic resonance (NMR) parameters such as nuclear magnetic shielding and indirect spin–spin coupling tensors. − There are also several works that emphasize the significant contribution of the electronic structure of the chiral center in enhancing PV effects, helping to understand which molecular structures are the best candidates toward experimental detection. , …”

Section: Introductionmentioning

confidence: 99%

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Electric Field Gradient in Chiral and Tetrahedral Molecules within High-Order LRESC Formalism

Aucar,

Melo,

Maldonado

2024

J. Phys. Chem. A

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In this work, we present the electric field gradient (EFG) given by the linear response elimination of the small component (LRESC) scheme up to the 1/c 4 order (c is the speed of light in vacuum) in CHFClX (X = Br, I, At) chiral molecules, together with CHF 2 Br and CH 2 FX (X = Br, I, At) tetrahedral systems. The former could be good candidates for further parity violation studies, especially when heavy atoms are surrounding. In this context, the LRESC scheme demonstrates effective applicability to large tetrahedral and chiral molecules that incorporate heavy elements, with relativistic effects playing a crucial role. The LRESC results of EFG exhibit an excellent agreement with those calculated at the four-component level, giving differences of only hundredths order in a.u. (atomic units) for the bromine nucleus and less than 0.1 a.u. for the iodine nucleus. Regarding the other nuclei, for the chiral molecules, there is a heavy atom effect on the light atom (HALA) for chlorine and fluorine atoms as the substituent halogen atom becomes heavier. Furthermore, the electronic part of the EFG for the central carbon and the fluorine nuclei presents an important dependence with the environment in the molecules under study. With accurate calculations of the EFG and tabulated nuclear quadrupole moment, the nuclear quadrupole coupling constant is obtained within the LRESC scheme, including for the first time correlation effects on the spin-dependent corrections with this methodology, providing results close to the experimental ones for Cl, Br, and I atoms. At the Hartree−Fock level, the differences are around 6% for Br and I nuclei, and at the density functional theory level with the LDA and PBE0 functionals, the differences are no more than 2%.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electric Field Gradient in Chiral and Tetrahedral Molecules within High-Order LRESC Formalism

Aucar,

Melo,

Maldonado

2024

J. Phys. Chem. A

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A relativistic relationship between parity-violating nuclear spin-rotation tensors and parity-violating NMR shielding tensors

Aucar

Jofre

Aucar

2023

The Journal of Chemical Physics

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The nuclear-spin-dependent parity-violation contributions to the NMR shielding and nuclear spin-rotation tensors ( σPV and MPV, respectively) are known to be formally related to one another in the non-relativistic regime. In this work, the polarization propagator formalism and the linear response within the elimination of small components model are used to show a new and more general relationship between them that is valid within the relativistic framework. The full set of the zeroth- and first-order relativistic contributions to σPV and MPV are also given here for the first time, and these results are compared with previous findings. According to four-component relativistic calculations, the electronic spin-orbit effects are the most significant ones for the isotropic values of σPV and MPV in the H2 X2 series of molecules (with X = O, S, Se, Te, and Po). When only scalar relativistic effects are taken into account, the non-relativistic relationship between σPV and MPV does hold. However, when spin-orbit effects are taken into consideration, this old non-relativistic relationship breaks down, and therefore the new one must be considered.

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Parity-violating contributions to nuclear spin-rotation interactions and to NMR shielding constants in tetrahedral molecules

Cited by 2 publications

References 105 publications

Electric Field Gradient in Chiral and Tetrahedral Molecules within High-Order LRESC Formalism

Electric Field Gradient in Chiral and Tetrahedral Molecules within High-Order LRESC Formalism

A relativistic relationship between parity-violating nuclear spin-rotation tensors and parity-violating NMR shielding tensors

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