Analysis of isotope effects in NMR one-bond indirect nuclear spin–spin coupling constants in terms of localized molecular orbitals

Literature Information

Publication Date 2009-03-03
DOI 10.1039/B819376B
Impact Factor 3.676
Authors

Patricio F. Provasi, Stephan P. A. Sauer


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Abstract

We recently showed, by analyzing contributions from localized molecular orbitals, that the anomalous deuterium isotope effect in the one-bond indirect nuclear spin–spin coupling constant of methane, also called the unexpected differential sensitivity, can be explained by the transfer of s-orbital character from the stretched bond to the other unchanged bonds [ChemPhysChem, 2008, 9, 1259]. We now extend this analysis of isotope effects to the molecules BH4−, NH4+, SiH4, H2O and NH3 in order to test our conclusions on a wider rage of XH4 compounds and to investigate whether the lone-pair orbitals are really responsible for the absence of a similar effect in water and ammonia as proposed earlier [J. Chem. Phys., 2000, 113, 3121].

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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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