PMID- 38230684
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20240207
IS  - 1463-9084 (Electronic)
IS  - 1463-9076 (Linking)
VI  - 26
IP  - 6
DP  - 2024 Feb 7
TI  - Machine learning-based correction for spin-orbit coupling effects in NMR chemical 
      shift calculations.
PG  - 4870-4884
LID - 10.1039/d3cp05556f [doi]
AB  - As one of the most powerful analytical methods for molecular and solid-state 
      structure elucidation, NMR spectroscopy is an integral part of chemical 
      laboratories associated with a great research interest in its computational 
      simulation. Particularly when heavy atoms are present, a relativistic treatment 
      is essential in the calculations as these influence also the nearby light atoms. 
      In this work, we present a Delta-machine learning method that approximates the 
      contribution to (13)C and (1)H NMR chemical shifts that stems from spin-orbit 
      (SO) coupling effects. It is built on computed reference data at the spin-orbit 
      zeroth-order regular approximation (ZORA) DFT level for a set of 6388 structures 
      with 38 740 (13)C and 64 436 (1)H NMR chemical shifts. The scope of the methods 
      covers the 17 most important heavy p-block elements that exhibit heavy atom on 
      the light atom (HALA) effects to covalently bound carbon or hydrogen atoms. 
      Evaluated on the test data set, the approach is able to recover roughly 85% of 
      the SO contribution for (13)C and 70% for (1)H from a scalar-relativistic 
      PBE0/ZORA-def2-TZVP calculation at virtually no extra computational costs. 
      Moreover, the method is transferable to other baseline DFT methods even without 
      retraining the model and performs well for realistic organotin and -lead 
      compounds. Finally, we show that using a combination of the new approach with our 
      previous Delta-ML method for correlation contributions to NMR chemical shifts, the 
      mean absolute NMR shift deviations from non-relativistic DFT calculations to 
      experimental values can be halved.
FAU - Kleine Buning, Julius B
AU  - Kleine Buning JB
AUID- ORCID: 0000-0001-7232-4897
AD  - Mulliken Center for Theoretical Chemistry, Clausius Institute for Physical and 
      Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany. 
      grimme@thch.uni-bonn.de.
FAU - Grimme, Stefan
AU  - Grimme S
AUID- ORCID: 0000-0002-5844-4371
AD  - Mulliken Center for Theoretical Chemistry, Clausius Institute for Physical and 
      Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany. 
      grimme@thch.uni-bonn.de.
FAU - Bursch, Markus
AU  - Bursch M
AUID- ORCID: 0000-0001-6711-5804
AD  - Max-Planck-Institut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mulheim an 
      der Ruhr, Germany. bursch@kofo.mpg.de.
LA  - eng
PT  - Journal Article
DEP - 20240207
PL  - England
TA  - Phys Chem Chem Phys
JT  - Physical chemistry chemical physics : PCCP
JID - 100888160
SB  - IM
EDAT- 2024/01/17 12:43
MHDA- 2024/01/17 12:44
CRDT- 2024/01/17 07:59
PHST- 2024/01/17 12:44 [medline]
PHST- 2024/01/17 12:43 [pubmed]
PHST- 2024/01/17 07:59 [entrez]
AID - 10.1039/d3cp05556f [doi]
PST - epublish
SO  - Phys Chem Chem Phys. 2024 Feb 7;26(6):4870-4884. doi: 10.1039/d3cp05556f.