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Title: An in-silico NMR laboratory for nuclear magnetic shieldings computed via finite fields: Exploring nucleus-specific renormalizations of MP2 and MP3

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/5.0145130 · OSTI ID:2293510
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [4]
  1. University of California, Berkeley, CA (United States). Department of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry
  2. University of California, Berkeley, CA (United States). Department of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; University of Bremen (Germany)
  3. University of California, Berkeley, CA (United States). Department of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; Columbia University, New York, NY (United States)
  4. University of California, Berkeley, CA (United States). Department of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
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Here we developed and implemented a method-independent, fully numerical, finite difference approach to calculating nuclear magnetic resonance shieldings, using gauge-including atomic orbitals. The resulting capability can be used to explore non-standard methods, given only the energy as a function of finite-applied magnetic fields and nuclear spins. For example, standard second-order Møller-Plesset theory (MP2) has well-known efficacy for 1H and 13C shieldings and known limitations for other nuclei such as 15N and 17O. It is, therefore, interesting to seek methods that offer good accuracy for 15N and 17O shieldings without greatly increased compute costs, as well as exploring whether such methods can further improve 1H and 13C shieldings. Using a small molecule test set of 28 species, we assessed two alternatives: κ regularized MP2 (κ-MP2), which provides energy-dependent damping of large amplitudes, and MP2.X, which includes a variable fraction, X, of third-order correlation (MP3). The aug-cc-pVTZ basis was used, and coupled cluster with singles and doubles and perturbative triples [CCSD(T)] results were taken as reference values. Our κ-MP2 results reveal significant improvements over MP2 for 13C and 15N, with the optimal κ value being element-specific. κ-MP2 with κ = 2 offers a 30% rms error reduction over MP2. For 15N, κ-MP2 with κ = 1.1 provides a 90% error reduction vs MP2 and a 60% error reduction vs CCSD. On the other hand, MP2.X with a scaling factor of 0.6 outperformed CCSD for all heavy nuclei. These results can be understood as providing renormalization of doubles amplitudes to partially account for neglected triple and higher substitutions and offer promising opportunities for future applications.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); German Research Foundation (DFG); National Energy Research Scientific Computing Center (NERSC)
Grant/Contract Number:
AC02-05CH11231; 5U01GM121667; STA 1526/1-1; STA 1526/2-1
OSTI ID:
2293510
Journal Information:
Journal of Chemical Physics, Vol. 158, Issue 16; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (5)

Table 1(p. 15)table Table 1
Table 2(p. 18)table Table 2
Figure 1(p. 21)figure Figure 1
Figure 2(p. 23)figure Figure 2
Table 3(p. 24)table Table 3

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Moller-Plesset perturbation theory
computational chemistry
correlation energy
correlation-consistent basis sets
shielding constants
finite difference methods
molecular properties
renormalization and regularization
quantum mechanical perturbation theory
nuclear magnetic resonance