Zero-point vibrational corrections to isotropic hyperfine coupling constants in polyatomic molecules
2011 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 13, no 2, 696-707 p.Article in journal (Refereed) Published
The present work addresses isotropic hyperfine coupling constants in polyatomic systems with a particular emphasis on a largely neglected, but a posteriori significant, effect, namely zero-point vibrational corrections. Using the density functional restricted-unrestricted approach, the zero-point vibrational corrections are evaluated for the allyl radical and four of its derivatives. In addition for establishing the numerical size of the zero-point vibrational corrections to the isotropic hyperfine coupling constants, we present simple guidelines useful for identifying hydrogens for which such corrections are significant. Based on our findings, we critically re-examine the computational procedures used for the determination of hyperfine coupling constants in general as well as the practice of using experimental hyperfine coupling constants as reference data when benchmarking and optimizing exchange-correlation functionals and basis sets for such calculations.
Place, publisher, year, edition, pages
RSC Publishing, 2011. Vol. 13, no 2, 696-707 p.
Physical Chemistry Atom and Molecular Physics and Optics
IdentifiersURN: urn:nbn:se:kth:diva-25886DOI: 10.1039/c0cp01443eISI: 000285390400041PubMedID: 21063618ScopusID: 2-s2.0-79953248258OAI: oai:DiVA.org:kth-25886DiVA: diva2:360464
FunderSwedish e‐Science Research Center
QC 20101103. Updated from manuscript to article in journal. 20111220 The published version of this article is deposited in DiVA by permission of the publisher. The pdf may however by no means be further made available or distributed.2010-11-032010-11-032012-05-23Bibliographically approved