The origin of hydrogen bonding. An energy decomposition study

Umeyama, Hideaki; Morokuma, Keiji

doi:10.1021/ja00447a007

Cited by 684 publications

(364 citation statements)

References 8 publications

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“…Its spectrum differs mainly by a broadening or split of the 3a 1 peak. This is typical for a two-dimensional H-bonded phase, which leads to peak splittings, because of different BEs of proton-acceptor and proton-donor molecules, as calculated for a H bonded dimer [339,340]. All acceptor orbitals are lowered with respect to the donor orbitals by the field of the positively charged bridging proton, leading to a splitting most clearly observable for the 3a 1 orbital.…”

Section: (I) Electronic Structures Of Adsorbatesmentioning

confidence: 83%

Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers

Weiß

Ranke

2002

Progress in Surface Science

579

610

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Metal-oxide based catalysts are used for many important synthesis reactions in the chemical industry. A better understanding of the catalyst operation can be achieved by studying elemantary reaction steps on well-defined model catalyst systems. For the dehydrogenation of ethylbenzene to styrene in the presence of steam both unpromoted and potassium promoted iron-oxide catalysts are active. Here we review the work done over unpromoted single-crystalline FeO(111), Fe 3 O 4 (111) and α-Fe 2 O 3 (0001) films grown epitaxially on Pt(111) substrates. Their geometric and electronic surface structures were characterized by STM, LEED, electron microscopy and electron spectroscopic techniques. In an integrative approach, the interaction of water, ethylbenzene and styrene with these films was investigated mainly by thermal desorption and photoelectron emission spectroscopy. The adsorptiondesorption energetics and kinetics depend on the oxide surface terminations and are correlated to the electronic structures and acid-base properties of the corresponding oxide phases, which reveal insight into the nature of the active sites and into the catalytic function of semiconducting oxides in general. Catalytic studies, using a batch reactor arrangement at high gas pressures and post reaction surface analysis, showed that only α-Fe 2 O 3 (0001) containing surface defects is catalytically active, whereas Fe 3 O 4 (111) is always inactive. This can be related to the elementary adsorption and desorption properties observed in ultrahigh vacuum, which indicates that the surface chemical properties of the iron-oxide films do not change significantly across the "pressure-gap". A model is proposed according to which the active site involves a regular acidic surface sites and a defect site next to it. The results on metal-oxide surface chemistry also have implications for other fields, such as environmental science, biophysics and chemical sensors.-2 -"2kyEi9FYSQjBVrZxIPQ.FHIAC_WRa02_review.doc", Datum: 19.02.03

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Section: (I) Electronic Structures Of Adsorbatesmentioning

confidence: 83%

Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers

Weiß

Ranke

2002

Progress in Surface Science

579

610

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“…There is a strong need to address this. These studies may aid the decomposition of anion interactions into more fundamental forces, c.f., hydrogen bonding decomposition by Morokuma, 93 or π-π decomposition stacking by Sherrill,94 such that it may be possible to determine the effects of 'turning down' Coulombic interactions and 'turning up' van der Waals interactions for a set anion geometry. This information would be key to understanding the interplay between receptor lipophilicity and anion binding in through-membrane transporters and channels.…”

Section: [Insert Figure 3]mentioning

confidence: 99%

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

et al. 2017

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Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry. AbstractOn planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapor and droplets fill the lower atmosphere; even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy, and computer modeling. More recently however, supramolecular chemistry -with its expertise in macrocyclic synthesis and measuring supramolecular interactions -have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offers to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups. 4Water is ubiquitous and essential to life on planet Earth. A full understanding of aqueous solutions is therefore of significance to a wide range of fields within the atmospheric, environmental, biological and geological sciences. Within the chemical sciences, a deeper appreciation of how non-covalent interactions and chemical transformations are influenced by water would benefit a variety of fields. However, as we highlight here, there are many open questions regarding the chemical and physical properties of aqueous solutions.The aqueous realm is frequently bifurcated into the Hofmeister and hydrophobic effects, phenomena that respectively deal with the properties of solutions of salts and relatively nonpolar molecules. However, it is becoming increasingly evident that these areas do in fact frequently overlap; two prime examples being the accumulation of large polarizable anions at the air-water interface, 1-5 and the favorable interactions of polarizable anions with non-polar surfaces. [6][7][8][9][10][11][12][13][14][15] Thus the hydrophobic and Hofmeister effects are but part of a greater continuum of aqueous supramolecular chemistry, with many important and outstanding questions regarding the influence of the different kinds of non-covalent interactions involved.Studies of water and aqueous solutions have mostly been driven by the physical sciences community, a broad range of scientists whose expertise in spectroscopy, computer modeling, and biochemistry (to name just three areas) has generally not involved macrocycles or host molecules in general. However, for some time now, supramolecular chemists -with their expertise in macrocyclic synthesis and measuring weak non-covalent interactions -have been travelling a parallel course of exploration. This Review, inspired by discussions between sixteen members of each community at a recent workshop, 16 is an attempt to summarize what we know about aqueous solutions, what we do not know about them, and where the two communit...

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“…During the past several decades, several EDA fragment-based approaches have been developed and used in a wide range of applications in chemistry. All of them have evolved from the early EDA of Kitaura and Morokuma [104][105][106]. These developments have taken place aiming to overcome limitations of the original schemes and provide more chemical significance to the energy components, which are not uniquely defined.…”

Section: Energy Decomposition Analysismentioning

confidence: 99%

Electronic structure theory to decipher the chemical bonding in actinide systems

Dognon

2017

Coordination Chemistry Reviews

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International audienceThe chemical bonding in actinide compounds is usually analysed by inspecting the shape and the occupation of the orbitals or by calculating bond orders which are based on orbital overlap and occupation numbers. However, this may not give a definite answer because the choice of the partitioning method may strongly influence the result possibly leading to qualitatively different answers. In this review, we summarized the state-of-the-art of methods dedicated to the theoretical characterisation of bonding including charge, orbital, quantum chemical topology and energy decomposition analyses. This review is not exhaustive but aims to highlight some of the ways opened up by recent methodological developments. Various examples have been chosen to illustrate this progress

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The origin of hydrogen bonding. An energy decomposition study

Cited by 684 publications

References 8 publications

Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers

Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Electronic structure theory to decipher the chemical bonding in actinide systems

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