Abstract
We generalize and unify Bleaney's theory and related inverse-temperature expansions of magnetic properties of paramagnetic species. Our approach is valid for different properties, including NMR chemical shifts beyond the point-dipole approximation, and for both transition-metal and lanthanide complexes. We derive an analytical equation for the 1/T[3] term. Furthermore, we implement higher-order terms numerically to investigate the convergence behavior of 1/T expansions. For transition-metal complexes, the second-order and third-order expansions provide quantitatively accurate results for most commonly encountered zero-field splittings. For an isostructural series of lanthanide complexes, the newly derived third-order term substantially improves the accuracy of calculated susceptibility anisotropies compared with Bleaney's second-order theory.
TY - JOUR
T1 - Generalization of Bleaney's Theory.
AU - Lang,Lucas,
AU - Lauw,Bryan,
AU - Fiorucci,Letizia,
Y1 - 2026/06/18/
PY - 2026/6/18/medline
PY - 2026/6/18/pubmed
PY - 2026/6/18/entrez
JF - The journal of physical chemistry. A
JO - J Phys Chem A
N2 - We generalize and unify Bleaney's theory and related inverse-temperature expansions of magnetic properties of paramagnetic species. Our approach is valid for different properties, including NMR chemical shifts beyond the point-dipole approximation, and for both transition-metal and lanthanide complexes. We derive an analytical equation for the 1/T[3] term. Furthermore, we implement higher-order terms numerically to investigate the convergence behavior of 1/T expansions. For transition-metal complexes, the second-order and third-order expansions provide quantitatively accurate results for most commonly encountered zero-field splittings. For an isostructural series of lanthanide complexes, the newly derived third-order term substantially improves the accuracy of calculated susceptibility anisotropies compared with Bleaney's second-order theory.
SN - 1520-5215
UR - https://www.unboundmedicine.com/prime/citation/42312827/Generalization_of_Bleaney's_Theory.
DB - PRIME
DP - Unbound Medicine
ER -
