Linking the Interatomic Exchange-Correlation Energy to Experimental J-Coupling Constants

The main aim of the current work is to find an experimental connection to the interatomic exchange-correlation energy as defined by the energy decomposition method Interacting Quantum Atoms (IQA). A suitable candidate as (essentially) experimental quantity is the nuclear magnetic resonance (NMR) J-coupling constant denoted 3J(H,H′), which a number of previous studies showed to correlate well with QTAIM’s delocalization index (DI), which is essentially a bond order. Inspired by Karplus equations, here, we investigate correlations between 3J(H,H′) and a relevant dihedral angle in six simple initial compounds of the shape H3C-YHn (Y = C, N, O, Si, P, and S), N- methylacetamide (as prototype of the peptide bond), and five peptide-capped amino acids (Gly, Ala, Val, Ile, and Leu) because of the protein direction of the force field FFLUX. In conclusion, except for methanol, the inter-hydrogen exchange-correlation energy Vxc(H,H′) makes the best contact with experiment, through 3J(H,H′), when multiplied with the internuclear distance RHH′.
This work was carried out with financial support from the Ministerio de Ciencia, Innovación y Universidades (PID2021- 125207NB-C32) and Comunidad de Madrid (P2018/EMT- 4329 AIRTEC-CM). Gratitude is due to the CTI (CSIC) for their continued computational support. P.L.A.P. acknowledges the EPSRC for funding through the award of an Established Career Fellowship (grant EP/K005472).