Exploring intra- and intermolecular interactions between non-covalently bound species through investigations of clusters: past, present, and future

Bernstein, E. R.; Bhattacharya, Atanu

doi:10.1016/b978-0-12-817586-6.00006-2

Intra- And Intermolecular Interactions Between Non-Covalently Bonded Species 2021

DOI: 10.1016/b978-0-12-817586-6.00006-2

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Exploring intra- and intermolecular interactions between non-covalently bound species through investigations of clusters: past, present, and future

E. R. Bernstein

Atanu Bhattacharya

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Cited by 2 publications

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A Cost Effective Scheme for the Highly Accurate Description of Intermolecular Binding in Large Complexes

Czernek

Brus

Czerneková

2022

IJMS

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There has been a growing interest in quantitative predictions of the intermolecular binding energy of large complexes. One of the most important quantum chemical techniques capable of such predictions is the domain-based local pair natural orbital (DLPNO) scheme for the coupled cluster theory with singles, doubles, and iterative triples [CCSD(T)], whose results are extrapolated to the complete basis set (CBS) limit. Here, the DLPNO-based focal-point method is devised with the aim of obtaining CBS-extrapolated values that are very close to their canonical CCSD(T)/CBS counterparts, and thus may serve for routinely checking a performance of less expensive computational methods, for example, those based on the density-functional theory (DFT). The efficacy of this method is demonstrated for several sets of noncovalent complexes with varying amounts of the electrostatics, induction, and dispersion contributions to binding (as revealed by accurate DFT-based symmetry-adapted perturbation theory (SAPT) calculations). It is shown that when applied to dimeric models of poly(3-hydroxybutyrate) chains in its two polymorphic forms, the DLPNO-CCSD(T) and DFT-SAPT computational schemes agree to within about 2 kJ/mol of an absolute value of the interaction energy. These computational schemes thus should be useful for a reliable description of factors leading to the enthalpic stabilization of extended systems.

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A Cost Effective Scheme for the Highly Accurate Description of Intermolecular Binding in Large Complexes

Czernek

Brus

Czerneková

2022

IJMS

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Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

et al. 2022

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Intra- and intermolecular interactions have been explored in selected N-oxide derivatives: 2-(N,N-dimethylamino-N-oxymethyl)-4,6-dimethylphenyl (1) and 5,5’-dibromo-3-diethylaminomethyl-2,2’-biphenol N-oxide (2). Both compounds possess intramolecular hydrogen bonding, which is classified as moderate in 1 and strong in 2, and resonance-assisted in both cases. Density Functional Theory (DFT) in its classical formulation as well as Time-Dependent extension (TD-DFT) were employed to study proton transfer phenomena. The simulations were performed in the gas phase and with implicit and explicit solvation models. The obtained structures of the studied N-oxides were compared with experimental data available. The proton reaction path was investigated using scan with an optimization method, and water molecule reorientation in the monohydrate of 1 was found upon the proton scan progress. It was found that spontaneous proton transfer phenomenon cannot occur in the electronic ground state of the compound 1. An opposite situation was noticed for the compound 2. The changes of nucleophilicity and electrophilicity upon the bridged proton migration were analyzed on the basis of Fukui functions in the case of 1. The interaction energy decomposition of dimers and microsolvation models was investigated using Symmetry-Adapted Perturbation Theory (SAPT). The simulations were performed in both phases to introduce polar environment influence on the interaction energies. The SAPT study showed rather minor role of induction in the formation of homodimers. However, it is worth noticing that the same induction term is responsible for the preference of water molecules’ interaction with N-oxide hydrogen bond acceptor atoms in the microsolvation study. The Natural Bond Orbital (NBO) analysis was performed for the complexes with water to investigate the charge flow upon the polar environment introduction. Finally, the TD-DFT was applied for isolated molecules as well as for microsolvation models showing that the presence of solvent affects excited states, especially when the N-oxide acceptor atom is microsolvated.

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Exploring intra- and intermolecular interactions between non-covalently bound species through investigations of clusters: past, present, and future

Cited by 2 publications

References 88 publications

A Cost Effective Scheme for the Highly Accurate Description of Intermolecular Binding in Large Complexes

A Cost Effective Scheme for the Highly Accurate Description of Intermolecular Binding in Large Complexes

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

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