Local energy decomposition analysis of hydrogen-bonded dimers within a domain-based pair natural orbital coupled cluster study

Abstract

The local energy decomposition (LED) analysis allows for a decomposition of the accurate domain-based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] energy into physically meaningful contributions including geometric and electronic preparation, electrostatic interaction, interfragment exchange, dynamic charge polarization, and London dispersion terms. Herein, this technique is employed in the study of hydrogen-bonding interactions in a series of conformers of water and hydrogen fluoride dimers. Initially, DLPNO-CCSD(T) dissociation energies for the most stable conformers are computed and compared with available experimental data. Afterwards, the decay of the LED terms with the intermolecular distance (r) is discussed and results are compared with the ones obtained from the popular symmetry adapted perturbation theory (SAPT). It is found that, as expected, electrostatic contributions slowly decay for increasing r and dominate the interaction energies in the long range. London dispersion contributions decay as expected, as r −6. They significantly affect the depths of the potential wells. The interfragment exchange provides a further stabilizing contribution that decays exponentially with the intermolecular distance. This information is used to rationalize the trend of stability of various conformers of the water and hydrogen fluoride dimers.

Three-dimensional docking of alcohols to ketones: an experimental benchmark based on acetophenone solvation energy balances

“…interaction with the phenyl side, whereas the experimentally observed structure focuses on the undistorted hydrogen bond. This can be qualitatively understood by analyzing the difference in D3 dispersion contribution between phenyl and alkyl docking at B3LYP level (see ESI, † Table S4, also for an analogous TPSS analysis) and alternatively by applying a LED 36,37 analysis at B3LYP and TPSS structures (see ESI, † Table S5). Rewardingly, all four analyses provide similar results.…”

Finding chemical concepts in the Hilbert space: Coupled cluster analyses of noncovalent interactions

“…For instance, this partitioning can be used to discuss intramolecular interactions or, more generally, any interaction for which single point energies on the isolated fragments are not feasible. Above all, the LED scheme has found widespread applications in the analysis of strong and weak intermolecular interactions within a supermolecular approach …”

“…For the dimers of Ar and water, is dominated by the dispersion component (in the water dimer case the situation changes in the long range, when electrostatics dominate the interaction; for the Ar dimer dispersion dominates the correlation for all interatomic distances, as discussed in Reference ). Interestingly, a numerical comparison between the LED and DFT‐SAPT estimates of the London dispersion energy for the water dimer case demonstrated that the two methods converge to the same values in the long range, while they slightly differ in the short range …”

London Dispersion Interactions in Pnictogen Cations [ECl2]+ and [E=E]2+ (E=P, As, Sb) Supported by Anionic N‐Heterocyclic Carbenes

“…To investigate the origin of the structural stability, reaction energies were also decomposed into dispersive (Δ E dis ) and non‐dispersive (Δ E −Δ E dis ) contributions. At the DLPNO‐CCSD(T) level, the decomposition was carried out through the local energy decomposition (LED) analysis using a two‐step procedure. Initially, the LED scheme was used to quantify the magnitude of the London dispersion energy contribution ( E dis ) associated with: 1) the L ⋅⋅⋅ECl 2 interaction in pnictogen dihalide compounds (reported in Table ); 2) the L ⋅⋅⋅ L and L ⋅⋅⋅E−E interactions in dipnictenes (reported in Table ).…”

“…Ta ble 3l ists the corresponding reaction energies (DE)c omputed at the DLPNO-CCSD(T) [52][53][54][55][56][57][58][59][60][61] and at the B3LYP-D3 (BJ) [62][63][64][65][66] levels of theory.T oi nvestigate the origin of the structural stability, reaction energiesw ere also decomposedi nto dispersive (DE dis )a nd non-dispersive (DEÀDE dis )c ontributions. At the DLPNO-CCSD(T) level, the decomposition was carried out through the local energy decomposition (LED) [48][49][50][51] analysis using at wo-stepp rocedure. Initially,t he LED schemew as used to quantify the magnitude of the Londond ispersion energy contribution (E dis )a ssociated with:1 )the L···ECl 2 interaction in pnictogen dihalide compounds (reported in Table 4);2 )the L···L and L···EÀEi nteractions in dipnictenes (reported in Ta ble 5).…”