An accurate benchmark description of the interactions between carbon dioxide and polyheterocyclic aromatic compounds containing nitrogen

Abstract

We assessed the performance of a large variety of modern density functional theory approaches for the adsorption of carbon dioxide on molecular models of pyridinic N-doped graphene. Specifically, we selected eight polyheterocyclic aromatic compounds ranging from pyridine and pyrazine to 1,6-diazacoronene and investigated their complexes with CO2 for a large range of intermolecular distances and including both in-plane and stacked orientations. The benchmark interaction energies were computed at the complete-basis-set limit MP2 level plus a CCSD(T) coupled-cluster correction in a moderate but carefully selected basis set. Using a set of 96 benchmark CCSD(T)-level interaction energies as a reference, we investigated the accuracy of DFT-based approaches as a function of the density functional, the dispersion correction, the basis set, and the counterpoise correction or lack thereof. While virtually all DFT variants exhibit some deterioration of accuracy for distances slightly shorter than the van der Waals minima, we were able to identify several schemes such as B2PLYP-D3 and M05-2X-D3 whose average errors on the entire benchmark data set are in the 5-10% range. The top DFT performers were subsequently used to investigate the energy profile for a carbon dioxide transition through model N-doped graphene pores. All investigated methods confirmed that the largest, N4H4 pore allows for a barrierless CO2 transition to the other side of a graphene sheet.

Aromatic Rings Commonly Used in Medicinal Chemistry: Force Fields Comparison and Interactions With Water Toward the Design of New Chemical Entities

“…Molecular mechanical (MM) topological parameters as bonds, angles, and Lennard-Jones parameters were taken from GROMOS53A6 (Oostenbrink et al, 2004 ). Due to the well–known good performance of MP2 methods for small aromatic rings (Li et al, 2015 ; Matczak and Wojtulewski, 2015 ), atomic partial charges were based on quantum mechanical (QM) calculations using MP2 theory (Møller and Plesset, 1934 ), 6-31G * (Petersson et al, 1988 ) basis set and implicit solvent Polarizable Continuum Model (PCM) (Mennucci and Tomasi, 1997 ) followed by a RESP fitting (Bayly et al, 1993 ). The so obtained partial charges were adjusted in the MM to reproduce the QM dipole moment of the ring.…”

Exploring the Limits of Second- and Third-Order Møller–Plesset Perturbation Theories for Noncovalent Interactions: Revisiting MP2.5 and Assessing the Importance of Regularization and Reference Orbitals

“…The CO2Nitrogen16 benchmark set includes 16 model complexes for the absorption of CO 2 onto eight polyheterocyclic aromatic compounds ranging from pyridine and pyrazine to 1,6-diazacoronene. However, we excluded the two largest diazacoronene data points due to difficulty obtaining MP3 energies for these systems.…”

“…The NCED data category includes 13 equilibrium geometry data sets: A24, DS14, HB15, HSG, S22, X40, HW30, NC15, S66, AlkBind12, CO2Nitrogen16, HB49, and Ionic43 . These data sets cover a wide range of different NCI motifs like classical hydrogen bonds, dispersion-bound systems, ionic interactions, and halogen bonding with various subclasses such as π-stacking, aliphatic dispersion, halogen−π, cyclic hydrogen bond, charged–neutral, and charged–charged ionic interactions; see Table for a short description of each data set.…”

ACCDB: A collection of chemistry databases for broad computational purposes

“…For more details of all the subsets of every database, as well as references to their original sources, and a better overview of their overlaps, see also the Supporting Information …”