Challenging Dogmas: Hydrogen Bond Revisited

Tafipolsky, Maxim

doi:10.1021/acs.jpca.6b04861

Cited by 26 publications

(34 citation statements)

References 129 publications

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“…The Wiberg bond indices for the halogen bond in the type 1 structures are 0.0192 and 0.0235 for X = I and At, respectively, that is, similar in magnitude as for the singly hydrates species. structures the non-bonded water hydrogen has moved to being nearly in plane (out-of-plane angles of 3 and 10 for I and At, respectively); thus there is a larger change, and therefore larger energy penalty, for AtPh-(H 2 O) 2 . This correlates with the smaller increase in interaction energy due to cooperativity for this system.…”

Section: Xph-(h 2 O) 2 Resultsmentioning

confidence: 99%

“…Fig. 1 2 , even though such a halogen bond was found in the singly hydrated species. The preference of forming a water dimer over separate interactions between the waters and the central molecule is consistent with previous work on microhydrated uracil, which showed that water molecules prefer to form two-and three-molecule water droplets binding to uracil, rather than distributing themselves over the different waterbinding sites.…”

Section: Comparison With Xmu-h 2 O and Xmu-(h 2 O)mentioning

confidence: 90%

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Halogen bonding in mono‐ and dihydrated halobenzene

Hogan

Mourik

2018

J Comput Chem

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Density functional theory calculations were performed on halogen‐bonded and hydrogen‐bonded systems consisting of a halobenzene (XPh; X = F, Cl, Br, I, and At) and one or two water molecules, using the M06‐2X density functional with the 6‐31+G(d) (for C, H, F, Cl, and Br) and aug‐cc‐pVDZ‐PP (for I, At) basis sets. The counterpoise procedure was performed to counteract the effect of basis set superposition error. The results show halogen bonds form in the XPh‐H2O system when X > Cl. There is a trend toward stronger halogen bonding as the halogen group is descended, as assessed by interaction energy and X•••Ow internuclear separation (where Ow is the water oxygen). For all XPh‐H2O systems hydrogen‐bonded systems exist, containing a combination of CH•••Ow and OwHw•••X hydrogen bonds. For all systems except X = At the X•••Hw hydrogen‐bonding interaction is stronger than the X•••Ow halogen bond. In the XPh‐(H2O)2 system halogen bonds form only for X > Br. The two water molecules prefer to form a water dimer, either located around the CH bond (for X = Br, At, and I) or located above the benzene ring (for all halogens). Thus, even in the absence of competing strong interactions, halogen bonds may not form for the lighter halogens due to (1) competition from cooperative weak interactions such as CH•••O and OH•••X hydrogen bonds, or (2) if the formation of the halogen bond would preclude the formation of a water dimer. © 2018 Wiley Periodicals, Inc.

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Section: Xph-(h 2 O) 2 Resultsmentioning

confidence: 99%

Section: Comparison With Xmu-h 2 O and Xmu-(h 2 O)mentioning

confidence: 90%

Halogen bonding in mono‐ and dihydrated halobenzene

Hogan

Mourik

2018

J Comput Chem

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“…34,91 Both in SAPT and GKS-EDA picture, the interaction is driven by the electrostatic (ELST) and dipole-dipole (IND and POL) interactions with only a small contribution from dispersion. The correlation term in GKS-EDA is indicated by (CORR).…”

Section: Figmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

101

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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“…It is often deemed to be an important and challenging task for a force field to correctly reproduce the directionality of hydrogen bonds. 43,50,94 Therefore, an assessment of the angular dependence of the water dimer interaction will be instructive. The angular scan is performed by modifying the θ angle illustrated in Figure 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Page 23 of 51 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 4...…”

Section: Journal Of Chemicalmentioning

confidence: 99%

Assessing Ion–Water Interactions in the AMOEBA Force Field Using Energy Decomposition Analysis of Electronic Structure Calculations

Mao

Demerdash

Head‐Gordon

et al. 2016

J. Chem. Theory Comput.

148

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AMOEBA is a molecular mechanics force field that addresses some of the shortcomings of a fixed partial charge model, by including permanent atomic point multipoles through quadrupoles, as well as many-body polarization through the use of point inducible dipoles. In this work, we investigate how well AMOEBA formulates its non-bonded interactions, and how it implicitly incorporates quantum mechanical effects such as charge penetration (CP) and charge transfer (CT), for water-water and water-ion interactions. We find that AMOEBA's total interaction energies, as a function of distance and over angular scans for the water dimer and for a range of water-monovalent cations, agree well with an advanced density functional theory (DFT) model, whereas the water-halides and water-divalent cations show significant disagreement with the DFT result, especially in the compressed region when the two fragments overlap. We use a second-generation energy decomposition analysis (EDA) scheme based on absolutely localized molecular orbitals (ALMOs) to show that in the best cases AMOEBA relies on cancellation of errors by softening of the van der Waals (vdW) wall to balance permanent electrostatics that are too unfavorable, thereby compensating for the missing CP effect. CT, as another important stabilizing effect not explicitly taken into account in AMOEBA, is also found to be incorporated by the softened vdW interaction. For the water-halides and water-divalent cations, this compensatory approach is not as well executed by AMOEBA over all distances and angles, wherein permanent electrostatics remains too unfavorable and polarization is overdamped in the former while overestimated in the latter. We conclude that the DFT-based EDA approach can help refine a next-generation AMOEBA model that either realizes a better cancellation of errors for problematic cases like those illustrated here, or serves to guide the parametrization of explicit functional forms for short-range contributions from CP and/or CT.

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Challenging Dogmas: Hydrogen Bond Revisited

Cited by 26 publications

References 129 publications

Halogen bonding in mono‐ and dihydrated halobenzene

Halogen bonding in mono‐ and dihydrated halobenzene

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Assessing Ion–Water Interactions in the AMOEBA Force Field Using Energy Decomposition Analysis of Electronic Structure Calculations

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