Evaluation of experimental alkali metal ion–ligand noncovalent bond strengths with DLPNO-CCSD(T) method

Abstract

We applied the domain based local pair natural orbital coupled cluster approach with single, double, and perturbative triple excitations, DLPNO-CCSD(T), to rationalize more than 130 experimental bond dissociation enthalpies collected in the work of Rodgers and Armentrout [Chem. Rev. 116, 5642-5687 (2016)] and involving alkali metal cations and versatile neutral organic and inorganic ligands ranging from common solvents to amino acids. In general, a remarkable agreement has been obtained between predicted and experimental alkali metal ionligand noncovalent bond strengths, highlighting a high degree of reliability of data assembled by Rodgers and Armentrout. In the case of some inconsistent experimental data given for some species, we pointed to a number for which best agreement with DLPNO-CCSD(T) calculations has been achieved. In addition, we refined a couple of ∆H 0 for which DLPNO-CCSD(T) values turned out to be significantly different from their experimental counterparts. We suggest an application of the DLPNO-CCSD(T) to derive the reference values to train/validate force field and neural network methods to be further applied in molecular dynamic simulations to unravel the mechanisms in biological systems and alkali metal ion batteries.

Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents

“…An experience suggests that reaction energies/enthalpies from the DLPNO-CCSD(T)/aug-cc-p(wC)VTZ//PBE-D3/ma-def2-svp protocol should be quite accurate. 103,104 Due to a wealth of low-lying frequencies in the solvent clusters, the entropy changes calculated for gas-phase reaction in Scheme 3 could be less reliable, yet leading to total errors in Δ * (( ) ) of only a few kcal/mol. For these reasons, the predicted in this work and utilized in equation ( 5) are most likely…”

Bootstrap Embedding For Large Molecular Systems

“…Since the pioneering works of Pulay and Saebo − in the 1980s, many research groups have contributed to this field, leading to the developments of a vast number of theories, as well as numerical techniques, including local Møller–Plesset perturbation theory to the second order , (LMP2), local coupled cluster theory − (LCC) and its orbital-specific virtual , (OSV) variant, Laplace transform MP2, , divide-and-conquer-based MP2 and CC , (DC-MP2 and CC), fragment molecular orbital − (FMO), and tensor hypercontraction − (THC), to name a few. We particularly mention the domain localized pair natural orbital − (DLPNO) approach, which represents one of the most popular local correlation methods that has been widely benchmarked − and used. − …”

Gas-Phase Thermochemistry of MX3 and M2X6 (M = Sc, Y; X = F, Cl, Br, I) from a Composite Reaction-Based Approach: Homolytic versus Heterolytic Cleavage

“…Given this background, we applied a reduced version of the Feller-Peterson-Dixon (FPD) [23][24][25][26] composite approach to derive gas-phase heats of formation and entropies of Sc/Y trihalides and their dimers. In line with our earlier studies, [27][28][29][30][31] for the sake of computational costs, we preferred the domain based local pair natural orbital coupled cluster approach with single, double, and perturbative triple excitations, DLPNO−CCSD(T), [32][33][34] in place of the standard unfavorably scaled CCSD(T) 35 approximation that is at the root of many composite schemes. [23][24][25][26][36][37][38] Indeed, we have demonstrated that reasonably accurate predictions (errors of 1-2 kcal/mol) of gas-phase thermochemistry of alloys and refractories decomposition products 27 and silver inorganic and organometallic systems, 28 as well as medium-size organic compounds, 29,31 can be obtained from the reaction-based DLPNO-CCSD(T) composite scheme.…”