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Title: Molecular NMR shieldings, J-couplings, and magnetizabilities from numeric atom-centered orbital based density-functional calculations

Journal Article · · Electronic Structure
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]
  1. Duke University, Durham, NC (United States); North Carolina State University
  2. North Carolina State University, Raleigh, NC (United States)
  3. Duke University, Durham, NC (United States)
  4. North Carolina State University, Raleigh, NC (United States); University of North Carolina at Chapel Hill, NC (United States)
+ Show Author Affiliations

This paper reports and benchmarks a new implementation of nuclear magnetic resonance shieldings, magnetizabilities, and J-couplings for molecules within semilocal density functional theory, based on numeric atom-centered orbital (NAO) basis sets. NAO basis sets are attractive for the calculation of these nuclear magnetic resonance (NMR) parameters because NAOs provide accurate atomic orbital representations especially near the nucleus, enabling high-quality results at modest computational cost. Moreover, NAOs are readily adaptable for linear scaling methods, enabling efficient calculations of large systems. Here, the paper has five main parts: (1) It reviews the formalism of density functional calculations of NMR parameters in one comprehensive text to make the mathematical background available in a self-contained way. (2) The paper quantifies the attainable precision of NAO basis sets for shieldings in comparison to specialized Gaussian basis sets, showing similar performance for similar basis set size. (3) The paper quantifies the precision of calculated magnetizabilities, where the NAO basis sets appear to outperform several established Gaussian basis sets of similar size. (4) The paper quantifies the precision of computed J-couplings, for which a group of customized NAO basis sets achieves precision of ~Hz for smaller basis set sizes than some established Gaussian basis sets. (5) The paper demonstrates that the implementation is applicable to systems beyond 1000 atoms in size.

Research Organization:
North Carolina State University, Raleigh, NC (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)
Grant/Contract Number:
SC0023334; AC02-05CH11231
OSTI ID:
2370384
Journal Information:
Electronic Structure, Journal Name: Electronic Structure Journal Issue: 2 Vol. 6; ISSN 2516-1075
Publisher:
IOP ScienceCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
97 MATHEMATICS AND COMPUTING
nuclear magnetic resonance
shieldings
magnetizabilities
J-couplings
molecules
semilocal density functional theory
numeric atom-centered orbital (NAO) basis sets