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The Journal of Chemical Physics
Article . 2013 . Peer-reviewed
Data sources: Crossref
https://dx.doi.org/10.48550/ar...
Article . 2012
License: arXiv Non-Exclusive Distribution
Data sources: Datacite
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NMR chemical shift as analytical derivative of the Helmholtz free energy

Authors: Van Den Heuvel W.; Soncini A.;

NMR chemical shift as analytical derivative of the Helmholtz free energy

Abstract

We present a theory for the temperature-dependent nuclear magnetic shielding tensor of molecules with arbitrary electronic structure. The theory is a generalization of Ramsey's theory for closed-shell molecules. The shielding tensor is defined as a second derivative of the Helmholtz free energy of the electron system in equilibrium with the applied magnetic field and the nuclear magnetic moments. This derivative is analytically evaluated and expressed as a sum over states formula. Special consideration is given to a system with an isolated degenerate ground state for which the size of the degeneracy and the composition of the wave functions are arbitrary. In this case, the paramagnetic part of the shielding tensor is expressed in terms of the g and A tensors of the electron paramagnetic resonance spin Hamiltonian of the degenerate state. As an illustration of the proposed theory, we provide an explicit formula for the paramagnetic shift of the central lanthanide ion in endofullerenes Ln@C60, with Ln = Ce3+, Nd3+, Sm3+, Dy3+, Er3+, and Yb3+, where the ground state can be a strongly spin-orbit coupled icosahedral sextet for which the paramagnetic shift cannot be described by previous theories.

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Italy
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Keywords

Chemical Physics (physics.chem-ph), Magnetic Resonance Spectroscopy, Temperature, FOS: Physical sciences, Electrons, Reference Standards, Lanthanoid Series Elements, Magnetic Fields, Physics - Chemical Physics, Quantum Theory, Fullerenes

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
79
Top 10%
Top 10%
Top 10%
Green
bronze