Relationships between interaction energy, intermolecular distance and electron density properties in hydrogen bonded complexes under external electric fields

How many tautomerization pathways connect Watson–Crick-like G*·T DNA base mispair and wobble mismatches?

“…The energies of the weak CH···O H-bonds [69,70] were calculated by the empirical Espinosa-Molins-Lecomte (EML) formula [71,72], which has been first successfully applied by C.F. Matta [73] for the estimation of the individual energetic contributions of the separate H-bonds in the two Watson-Crick DNA base pairs:…”

“…c The Laplacian of the electron density at the (3,-1) BCP of the H-bond, a.u. d The ellipticity at the (3,-1) BCP of the H-bond e The distance between the A (H-bond donor) and B (H-bond acceptor) atoms of the AH···B H-bond, Å f The distance between the H and B atoms of the AH···B H-bond, Å g The elongation of the H-bond donating group AH upon the AH···B H-bonding, Å h The H-bond angle, º i The redshift of the stretching vibrational mode ν(AH) of the AH H-bonded group, cm -1 jEnergy of the H-bonds, calculated by Iogansen's[74], Espinose-Molins-Lecomte (marked with an asterisk)[71,72] and Nikolaienko-Bulavin-Hovorun (marked with double asterisk)[75] formulas, kcal·mol -1 k The dipole moment of the complex, D § Data are taken from the work[2] and § § data are taken from the work[17].…”

Wobble↔Watson-Crick tautomeric transitions in the homo-purine DNA mismatches: a key to the intimate mechanisms of the spontaneous transversions

“…In this case, the value of the effective dielectric constant ε (1 < ε < 4), that is characteristic for the anhydrous molecular crystals, satisfactorily models the substantially hydrophobic recognition pocket of the DNApolymerase machinery as a part of the replisome and can be approximated by vacuum [46]. [38] or Espinose-Molins-Lecomte (marked with an asterisk) [36,37] formulas, kcal•mol -1 ; j The relative Gibbs free energy of the complex obtained at the MP2/cc-pVQZ//B3LYP/6-311++G(d,p) level of theory under normal conditions, kcal•mol -1 ; k The dipole moment of the complex, D. Table S2. Energetic and kinetic characteristics of the A•A(w)↔A*·A(WC), A·A syn↓ (w)↔A*·A syn (TF) and A·A syn↑ (w)↔A*·A syn (TF) tautomerisations via the sequential DPT obtained at the different levels of theory for the geometry calculated at the B3LYP/6-311++G(d,p) level of theory (see also Figs.…”

The Paradox of Hydrogen-Bonded Anion–Anion Aggregates in Oxoanions: A Fundamental Electrostatic Problem Explained in Terms of Electrophilic···Nucleophilic Interactions

“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 In order to estimate better the effect of the PCM on the interaction energy, E i can be compared with the energy of the hydrogen bond (E HB ), which can be estimated from the topology of ρ(r). 49,50 If the interaction energy in the complexes is exclusively due to hydrogen bonding, E i should be approximately 2E HB . Indeed, most the complexes of the protic and salt complexes in gas phase fall close the line E i = 2E HB (Figure 11),…”