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Optimizing Molecular Geometries in Strong Magnetic Fields

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Professor of Computational and Theoretical Chemistry


An efficient implementation of geometrical derivatives at the Hartree-Fock (HF) and current-density-functional theory (CDFT) levels is presented for the study of molecular structure in strong magnetic fields. The required integral derivatives are constructed using a hybrid McMurchie-Davidson and Rys quadrature approach, which combines the amenability of the former to the evaluation of derivative integrals with the efficiency of the latter for basis sets with high angular momentum. In addition to its application to evaluating derivatives of four-centre integrals, this approach is also applied to gradients using the resolution-of-the-identity approximation, enabling efficient optimization of molecular structure for many-electron systems under a strong magnetic field. The CDFT contributions have been implemented for a wide range of density-functionals up to and including the meta-GGA level with current-density dependent contributions and (range-separated) hybrids for the first time. Illustrative applications are presented to the OH and benzene molecules, revealing the rich and complex chemistry induced by the presence of an external magnetic field. Challenges 1 for geometry optimization in strong fields are highlighted, along with the requirement for careful analysis of the resulting electronic structure at each stationary point. The importance of correlation effects is examined by comparison of results at the HF and CDFT levels. The present implementation of molecular gradients at the CDFT level provides a cost-effective approach to the study of molecular structure under strong magnetic fields, opening up many new possibilities for the study of chemistry in this regime.


Irons, T. J. P., David, G., & Teale, A. M. (2021). Optimizing Molecular Geometries in Strong Magnetic Fields. Journal of Chemical Theory and Computation, 17(4), 2166–2185.

Journal Article Type Article
Acceptance Date Feb 2, 2021
Online Publication Date Mar 16, 2021
Publication Date Apr 13, 2021
Deposit Date Feb 9, 2021
Publicly Available Date Mar 16, 2021
Journal Journal of Chemical Theory and Computation
Print ISSN 1549-9618
Electronic ISSN 1549-9626
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 17
Issue 4
Pages 2166–2185
Keywords Physical and Theoretical Chemistry; Computer Science Applications
Public URL
Publisher URL


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