Molecular Orbital Studies of Hydrogen Bonds. III. C=O···H–O Hydrogen Bond in H2CO···H2O and H2CO···2H2O

Abstract

Ab initio LCAO–MO–SCF calculation for H2CO···H2O is carried out with a minimal Slater basis set. The most stable conformation has an O···H distance of 1.89 Å with <C=O···H=− 64° and a stabilization energy of 3.5 kcal/mole, about a half of that for H2O···H2O. Nonlinear and π hydrogen bonds, H2CO···2H2O and the O···H–C hydrogen bond in H2O···HCHO, are also studied. An energy decomposition scheme is proposed and applied to H2CO···H2O and H2O···H2O. In the latter the electrostatic energy 8.0 kcal/mole, the exchange repulsion − 9.9 kcal/mole, the polarization and dispersion energy 0.3 kcal/mole, and the delocalization energy 8.2 kcal/mole are in good agreement with Coulson's estimates.

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

“…The bonding situation of the metal-carbene bonds was investigated by an energy decomposition analysis (EDA) which was developed by Morokuma 87 and by Ziegler and Rauk. 88,89 The bonding analysis focuses on the instantaneous interaction energy ΔE int of a 90 It comprises the destabilizing interactions between electrons of the same spin on either fragment.…”

Phospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes

“…53,54 Energy decomposition analyses for optimized structures were performed with the ADF 2007.01 program. 55 The analysis followed the Morokuma-RaukZiegler partition scheme [56][57][58] and utilized the PBEPBE GGA functional [47][48][49] in combination with STO-type all-electron basis sets of TZP quality. 59,60 Scalar relativistic effects were taken into account in all EDA calculations by employing the ZORA Hamiltonian.…”

“…To the best of our knowledge, there are no reports of an energy decomposition analysis (EDA) of M-NHP bonding within the framework of a fragment molecular orbital (FMO) approach. [56][57][58] This combination of methods is aptly suited for the analysis of donor-acceptor interactions because it allows a simple quantification of the relative importance of -and -contributions to bonding.…”

Pair interaction energy decomposition analysis

“…One of the earlier approaches to the analysis of binding has been proposed by Morokuma 1 and further extended by Kitaura and Morokuma. 2 Their energy decomposition approach (EDA, also called sometimes the KM analysis) has become standard [3][4][5] and has been widely used during the 30 years since its appearance.…”