Illumination of the effect of the overlap of lone-pairs on indirect nuclear spin–spin coupling constants

Literature Information

Publication Date 2011-08-08
DOI 10.1039/C1CP21422E
Impact Factor 3.676
Authors

Olga L. Malkina, Anežka Křístková, Elena Malkin, Stanislav Komorovský, Vladimir G. Malkin


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Abstract

The effect of electron lone-pairs on the Fermi-contact (FC) contribution to indirect nuclear spin–spin coupling constants is analyzed using new tools for their interpretation. In particular, visualization of spin–spin coupling pathways using the coupling deformation density (CDD) has been employed. Furthermore, the recently developed perturbation-stable localization procedure has been applied for decomposition of CDD and the calculated value of couplings into contributions from localized molecular orbitals (LMOs). Correlation between the overlap of densities of LMOs representing lone-pairs and the Fermi-contact contribution to spin–spin coupling constants has been demonstrated. A new way for analyzing spin–spin couplings using the expansion of CDD as a linear combination of the products of molecular orbitals has been suggested. The considered examples include two- and three-bond phosphor–phosphor couplings. Significance of the obtained insight is not restricted to spin–spin couplings of nuclei possessing lone-pairs, as demonstrated in the example of vicinal hydrogen–hydrogen coupling in ethane.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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