Exactly Fragment Additive Breakdown of Polarization for Energy Decomposition Analysis Based on the Self-Consistent Field for Molecular Interactions

Quantum chemical modeling of hydrogen binding in metal–organic frameworks: validation, insight, predictions and challenges

“…Moreover, its ΔPol counterpart is also remarkably large and attractive compared to the first and third hydrogens. We turned to the recently developed polarization analysis 137 to seek an explanation, resulting in the POL COVPs shown in Fig. 16.…”

Occupied-Virtual Orbitals for Chemical Valence with Applications to Charge Transfer in Energy Decomposition Analysis

“…We shall show that the sum of these values is also exactly the same as the excitation number . Though this is a general theory between any two single-determinant electronic states, we limit our analysis to the CT process in forming molecular complexes, since this eliminates the polarization effect and makes the donor–acceptor orbitals more obvious, while the polarization process can be analyzed with COVPs if desired.…”

Demystifying hydridic hydrogen bonds using energy decomposition analysis

“…From Table S1, we found that in general, POL and CT are stronger in the hydridic HBs to σ -hole compounds than in other types. To achieve a more detailed understanding of the POL and CT effects involved in hydridic HBs, we applied the recently developed non-perturbative POL and CT analysis 8,9 that are associated with ALMO-EDA, and compared the results to those of protonic HBs. This analysis not only provides a fragmentwise breakdown of the total POL and CT energies (see SI Table S4) but also provides an orbital-based depiction of the POL and CT processes by computing and visualizing the complementary occupied-virtual pairs (COVPs), 8,9,27 which can be interpreted as the most significant changes in orbitals induced by POL/CT.…”