Is the Hydrogen Bond in Water Dimer and Ice Covalent?

Ghanty, Tapan K.; Staroverov, Viktor N.; Koren, and Patrick R.; Davidson, Ernest R.

doi:10.1021/ja9937019

Cited by 178 publications

(162 citation statements)

References 29 publications

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“…Although DFT does not reproduce the absolute momentum density correctly, [87][88][89][90][91] it often reproduces these differences well, [90,92,93] hybrid functionals likely faring better than pure functionals. [90] Figure 1.…”

Section: Emd and Compton Profilementioning

confidence: 99%

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

et al. 2012

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ERKALE is a novel software program for computing X-ray properties, such as ground-state electron momentum densities, Compton profiles, and core and valence electron excitation spectra of atoms and molecules. The program operates at Hartree-Fock or density-functional level of theory and supports Gaussian basis sets of arbitrary angular momentum and a wide variety of exchange-correlation functionals. ERKALE includes modern convergence accelerators such as Broyden and ADIIS and it is suitable for general use, as calculations with thousands of basis functions can routinely be performed on desktop computers. Furthermore, ERKALE is written in an object oriented manner, making the code easy to understand and to extend to new properties while being ideal also for teaching purposes.

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Section: Emd and Compton Profilementioning

confidence: 99%

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

et al. 2012

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“…approaches 19,59 and the linear-scaling EDA of Phipps et al 60 ) and their ability to treat many-fragment systems, 61 they are instrumental in the continuing effort to better understand liquid water and ice, [62][63][64] cooperative effects, 25,[65][66][67][68] and other interactions in solution. 69,70 Moreover, they treat both inter-and intramolecular 18,19,43,71 (including through-bond) interactions on equal footing (including through bond) and, thus, capably describe phenomena that are of a mixed or non-covalent nature, e.g., dative bonds, 27,72,73 as well as chemisorption and physisorption processes 221,222 (through a "periodic EDA" by Tonner et al 223 ).…”

Section: Figmentioning

confidence: 99%

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

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

110

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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“…An alternative approach is to examine changes in other molecular properties such as charge and momentum distributions. 25 These methods, however, are applicable to the study of intermolecular interactions but not the resonance effect, which is an intramolecular phenomenon. The concept of resonance came up when one Lewis (resonance) structure was not enough to describe a conjugated system.…”

Section: Introductionmentioning

confidence: 99%

How resonance assists hydrogen bonding interactions: An energy decomposition analysis

Beck

2006

J Comput Chem

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Block-localized wave function (BLW) method, which is a variant of the ab initio valence bond (VB) theory, was employed to explore the nature of resonance-assisted hydrogen bonds (RAHBs) and to investigate the mechanism of synergistic interplay between delocalization and hydrogen-bonding interactions. We examined the dimers of formic acid, formamide, 4-pyrimidinone, 2-pyridinone, 2-hydroxpyridine, and 2-hydroxycyclopenta-2,4-dien-1-one. In addition, we studied the interactions in -diketone enols with a simplified model, namely the hydrogen bonds of 3-hydroxypropenal with both ethenol and formaldehyde. The intermolecular interaction energies, either with or without the involvement of resonance, were decomposed into the Hitler-London energy (DE HL ), polarization energy (DE pol ), charge transfer energy (DE CT ), and electron correlation energy (DE cor ) terms. This allows for the examination of the character of hydrogen bonds and the impact of conjugation on hydrogen bonding interactions. Although it has been proposed that resonance-assisted hydrogen bonds are accompanied with an increasing of covalency character, our analyses showed that the enhanced interactions mostly originate from the classical dipoledipole (i.e., electrostatic) attraction, as resonance redistributes the electron density and increases the dipole moments in monomers. The covalency of hydrogen bonds, however, changes very little. This disputes the belief that RAHB is primarily covalent in nature. Accordingly, we recommend the term ''resonance-assisted binding (RAB)'' instead of ''resonance-assisted hydrogen bonding (RHAB)'' to highlight the electrostatic, which is a long-range effect, rather than the electron transfer nature of the enhanced stabilization in RAHBs.

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Is the Hydrogen Bond in Water Dimer and Ice Covalent?

Cited by 178 publications

References 29 publications

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

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

How resonance assists hydrogen bonding interactions: An energy decomposition analysis

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