Journal
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
Volume 87, Issue 7, Pages 927-941Publisher
CANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESS
DOI: 10.1139/V09-040
Keywords
density functional theory; relativistic effects; spin-spin coupling constant; dipolar coupling; rovibrational averaging; alkali metal halides; group-17 fluorides; xenon fluorides
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Funding
- Natural Sciences and Engineering Research Council of Canada (NSERC)
- National Science Foundation [CHE-0447321]
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The accurate calculation of the isotropic (J(iso)) and anisotropic (Delta J) parts of indirect nuclear spin-spin coupling tensors is a stringent test for quantum chemistry, particularly for couplings involving heavy isotopes where relativistic effects and relativity - electron correlation cross terms are expected to play an important role. Experimental measurements on diatomic molecules in the gas phase offer ideal data for testing the success of computational approaches, since the data are essentially free from intermolecular effects, and precise coupling anisotropies may be reliably extracted in favourable cases. On the basis of available experimental molecular-beam coupling-tensor parameters for diatomic alkali metal halides, we tabulate known values of J(iso) and, taking rotational-vibrational corrections to the direct dipolar coupling constant into account, precise values of Delta J are determined for the ground rovibrational state. First-principles calculations of the coupling tensors were performed using a recently developed program based on hybrid density functional theory using the two-component relativistic zeroth-order regular approximation (ZORA). Experimental trends in J(iso) and Delta J are reproduced with correlation coefficients of 0.993 and 0.977, respectively. Periodic trends in the coupling constants and their dependence on the product of the atomic numbers of the coupled nuclei are discussed. Finally, the hybrid functional method is also successfully tested against experimental data for a series of polyatomic xenon fluorides and group-17 fluorides
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