Evaluation of Theoretical Approaches for Describing the Interaction of Water with Linear Acenes

Abstract

The interaction of a water monomer with a series of linear acenes (benzene, anthracene, pentacene, heptacene, and nonacene) is investigated using a wide range of electronic structure methods, including several "dispersion"-corrected density functional theory (DFT) methods, several variants of the random phase approximation (RPA), DFT-based symmetry-adapted perturbation theory with density fitting (DF-DFT-SAPT), MP2, and coupled-cluster methods. The DF-DFT-SAPT calculations are used to monitor the evolution of the electrostatics, exchange-repulsion, induction, and dispersion contributions to the interaction energies with increasing acene size and also provide the benchmark data against which the other methods are assessed.

A molecular-level computational study of the diffusion and solubility of water and oxygen in carbonaceous polyethylene nanocomposites

“…The AMBER binding energy between a water molecule and a (3, 3)SWCNT [similar to the (3, 3)SWCNT used for the AMBER validation described above] is between −4.6 to −5.0 kJ mol −1 . This is slightly less than previously reported interaction strengths of −6.8 to −14.0 kJ mol −1 between a water molecule and graphene‐like surfaces . Consequently, the calculated solubility coefficient of water might be slightly underestimated and the diffusion coefficient slightly overestimated for the systems containing graphene or a SWCNT; however, the obtained trends in solubility and diffusion coefficients of water with increasing temperatures are not expected to be affected.…”

“…This is slightly less than previously reported interaction strengths of 26.8 to 214.0 kJ mol 21 between a water molecule and graphene-like surfaces. 57,58 Consequently, the calculated solubility coefficient of water might be slightly underestimated and the diffusion coefficient slightly overestimated for the systems containing graphene or a SWCNT; however, the obtained trends in solubility and diffusion coefficients of water with increasing temperatures are not expected to be affected. In contrast, the intermolecular interaction between oxygen molecules is negligible in the gas phase (it behaves as an ideal gas), and the binding strength between the additive and the oxygen may therefore attract oxygen into the composite.…”

Resolution-of-identity approach to Hartree–Fock, hybrid density functionals, RPA, MP2 andGWwith numeric atom-centered orbital basis functions

“…We believe that the well-converged numbers reported in this work may serve as benchmarks for future studies. Beyond the specific examples given here, our RI framework as a whole has already proven to be stable and mature in a number of scientific applications [40,41,96,176,[206][207][208]. Based on the results above, NAOs emerge as a promising route towards more compact basis sets for correlated methods.…”

Theory and practice of modeling van der Waals interactions in electronic-structure calculations

“…129 In MP2C, the dispersion energy based on uncoupled HF of KS states is replaced with the dispersion components calculated in the corresponding coupled perturbation formalism, which has been shown to significantly improve interaction energies for dispersion bound systems. [130][131][132] Another successful application is the use of SAPT-derived potential energy surfaces (PESs), where the PES is calculated on a representative grid using SAPT(@DFT). This PES is then interpolated at runtime to perform, e.g., extended molecular dynamics simulations with quantumchemical accuracy nearly at the cost of molecular mechanics, which has been proven a viable tool for studying simple biomolecular assemblies, vdW complexes, crystal structures, or condensed phase systems, for instance.…”