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Assessment of Density Functional Theory in Predicting Interaction Energies Between Water and Polycyclic Aromatic Hydrocarbons: From Water on Benzene to Water on Graphene

Ajala, Adeayo O. and Voora, Vamsee K. and Mardirossian, Narbe and Furche, Filipp and Paesani, Francesco (2019) Assessment of Density Functional Theory in Predicting Interaction Energies Between Water and Polycyclic Aromatic Hydrocarbons: From Water on Benzene to Water on Graphene. Journal of Chemical Theory and Computation, 15 (4). pp. 2359-2374. ISSN 1549-9618. http://resolver.caltech.edu/CaltechAUTHORS:20190312-135349638

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Abstract

The interactions of water with polycyclic aromatic hydrocarbons, from benzene to graphene, are investigated using various exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. The accuracy of the different functionals is assessed through comparisons with random phase approximation (RPA) and coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] calculations. Diffusion Monte Carlo (DMC) data reported in the literature are also used for comparison. Relatively large variations are found in interaction energies predicted by different DFT models, with GGA functionals underestimating the interaction strength for configurations with the water oxygen pointing toward the aromatic molecules. The meta-GGA B97M-rV and range-separated hybrid, meta-GGA ωB97M-V functionals provide nearly quantitative agreement with CCSD(T) values for the water–benzene, water–coronene, and water–circumcoronene dimers, while RPA and DMC predict interaction energies that differ by up to ∼1 kcal/mol and ∼0.4 kcal/mol from the corresponding CCSD(T) values, respectively. Similar trends among GGA, meta-GGA, and hybrid functionals are observed for larger polycyclic aromatic hydrocarbons. By performing absolutely localized molecular orbital energy decomposition analyses (ALMO-EDA), it is found that, independently of the number of carbon atoms and exchange-correlation functional, the dominant contributions to the interaction energies between water and polycyclic aromatic hydrocarbon molecules are the electrostatic and dispersion terms while polarization and charge transfer effects are negligibly small. Calculations carried out with GGA and meta-GGA functionals indicate that, as the number of carbon atoms increases, the interaction energies slowly converge to the corresponding values obtained for an infinite graphene sheet.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jctc.9b00110DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.jctc.9b00110PublisherSupporting Information
ORCID:
AuthorORCID
Furche, Filipp0000-0001-8520-3971
Paesani, Francesco0000-0002-4451-1203
Additional Information:© 2019 American Chemical Society. Received: February 2, 2019; Published: March 12, 2019. This research was supported by the National Science Foundation through grant no. CHE-1453204 and the Air Force Office of Scientific Research through grant no. FA9550-16-1-0327 awarded to F.P. (DFT and L-CCSD(T) calculations) and the National Science Foundation through grant no. CHE-1800431 awarded to F.F. (RPA calculations). We used computational resources of the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation through grant no. ACI-1053575 under allocation TG-CHE110009, as well as of the Department of Defense. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1453204
Air Force Office of Scientific Research (AFOSR)FA9550-16-1-0327
NSFCHE-1800431
NSFACI-1053575
NSFTG-CHE110009
Department of DefenseUNSPECIFIED
Record Number:CaltechAUTHORS:20190312-135349638
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190312-135349638
Official Citation:Assessment of Density Functional Theory in Predicting Interaction Energies between Water and Polycyclic Aromatic Hydrocarbons: from Water on Benzene to Water on Graphene. Adeayo O. Ajala, Vamsee Voora, Narbe Mardirossian, Filipp Furche, and Francesco Paesani. Journal of Chemical Theory and Computation 2019 15 (4), 2359-2374. DOI: 10.1021/acs.jctc.9b00110
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93739
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Mar 2019 21:10
Last Modified:11 Apr 2019 17:05

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