Performance of Several Density Functional Theory Methods on Describing Hydrogen-Bond Interactions

Rao, Li; Ke, Hongwei; Fu, Gang; Xu, Xin; Yan, YiJing

doi:10.1021/ct800237n

Cited by 135 publications

(107 citation statements)

References 50 publications

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“…A recent study has analyzed how well different functionals describe hydrogen-bonding interactions. [95] We find the C s structure to be the minimum (though, as the numbers in Figure 7 show, the hydrogen bond is found to be about 1 kcal mol À1 weaker than the best computed values), with an H1ÀN1···N2 angle of 8.78. The difference in energy between the equilibrium and transition state structure is 0.2 kcal mol À1 .…”

Section: Hydrogen Bondingmentioning

confidence: 68%

A Molecular Perspective on Lithium–Ammonia Solutions

2009

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A detailed molecular orbital (MO) analysis of the structure and electronic properties of the great variety of species in lithium-ammonia solutions is provided. In the odd-electron, doublet states we have considered: e-@(NH3)n (the solvated electron, likely to be a dynamic ensemble of molecules), the Li(NH3)4 monomer, and the [Li(NH3)4+.e-@(NH3)n] ion-pairs, the Li 2s electron enters a diffuse orbital built up largely from the lowest unoccupied MOs of the ammonia molecules. The singly occupied MOs are bonding between the hydrogen atoms; we call this stabilizing interaction H-->H bonding. In e-@(NH3)n the odd electron is not located in the center of the cavities formed by the ammonia molecules. Possible species with two or more weakly interacting electrons also exhibit H-->H bonding. For these, we find that the singlet (S=0) states are slightly lower in energy than those with unpaired (S=1, 2...) spins. TD-DFT calculations on various ion-pairs show that the three most intense electronic excitations arise from the transition between the SOMO (of s pseudosymmetry) into the lowest lying p-like levels. The optical absorption spectra are relatively metal-independent, and account for the absorption tail which extends into the visible. This is the source of Sir Humphry Davy's "fine blue colour" first observed just over 200 years ago.

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Section: Hydrogen Bondingmentioning

confidence: 68%

A Molecular Perspective on Lithium–Ammonia Solutions

2009

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“…These methods are similar in some ways to ab initio approaches, with the major distinction that DFT considers all molecular orbitals at one time, via the total electron density, which leads to their greater efficiency. They have been applied to hydrogen bonds at an accelerating pace [161][162][163][164][165][166][167], beginning in the early 1990s. Their major deficiencies lie first in their failure to include dispersion forces in a systematic manner; there are ongoing efforts [168][169][170] to correct this problem, particularly since dispersion can be one of the major contributors to hydrogen bonding.…”

Section: Theoretical/computational Methodsmentioning

confidence: 99%

Defining the hydrogen bond: An account (IUPAC Technical Report)

Arunan

Desiraju

Klein³

et al. 2011

Pure and Applied Chemistry

916

622

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Abstract:The term "hydrogen bond" has been used in the literature for nearly a century now. While its importance has been realized by physicists, chemists, biologists, and material scientists, there has been a continual debate about what this term means. This debate has intensified following some important experimental results, especially in the last decade, which questioned the basis of the traditional view on hydrogen bonding. Most important among them are the direct experimental evidence for a partial covalent nature and the observation of a blue-shift in stretching frequency following X-HؒؒؒY hydrogen bond formation (XH being the hydrogen bond donor and Y being the hydrogen bond acceptor). Considering the recent experimental and theoretical advances, we have proposed a new definition of the hydrogen bond, which emphasizes the need for evidence. A list of criteria has been provided, and these can be used as evidence for the hydrogen bond formation. This list is followed by some characteristics that are observed in typical hydrogen-bonding environments.

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“…In the VASP calculations, the Perdew, Burke, and Ernzerhof (PBE) functional was used to describe electronic exchange and correlation (31). Previous studies confirmed that the PBE functional is suitable for describing hydrogen-bond interactions (32)(33)(34)(35), together with metal-oxygen bond interactions. All calculations for optimizing PB nanoribbon structures were spin polarized.…”

Section: Methodsmentioning

confidence: 99%

One-dimensional nanowires of pseudoboehmite (aluminum oxyhydroxide γ-AlOOH)

Iijima

Yumura

Liu

2016

Proc. Natl. Acad. Sci. U.S.A.

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We report the discovery of a 1D crystalline structure of aluminum oxyhydroxide. It was found in a commercial product of fibrous pseudoboehmite (PB), γ-AlOOH, synthesized easily with low cost. The thinnest fiber found was a ribbon-like structure of only two layers of an Al-O octahedral double sheet having a submicrometer length along its c axis and 0.68-nm thickness along its b axis. This thickness is only slightly larger than half of the lattice parameter of the b-axis unit cell of the boehmite crystal (b/2 = 0.61 nm). Moreover, interlayer splittings having an average width of 1 nm inside the fibrous PB are found. These wider interlayer spaces may have intercalation of water, which is suggested by density functional theory (DFT) calculation. The fibers appear to grow as almost isolated individual filaments in aqueous Al-hydroxide sols and the growth direction of fibrous PB is always along its c axis.ow-dimensional materials such as quantum dots (1), nanowires (2, 3), and nanosheets (4) have attracted interest in academia and industry. Carbon nanotubes (5), a typical 1D inorganic material, have been investigated widely, but new 1D inorganic materials prepared by a simple and reliable method have rarely been reported.The aluminum ore bauxite primarily comprises aluminum hydroxide possessing different crystalline forms. The thermal dehydration of aluminum hydroxide produces alumina Al 2 O 3, one of the most important materials in modern industries. γ-Boehmite (γ-AlOOH) (6) is a typical aluminum oxyhydroxide with a crystal structure similar to that of lepidocrocite (γ-FeOOH) (7). These metal oxyhydroxides, represented by γ-MO(OH), where M = Fe, Ni, Mn, Sc, Ti, etc., have attracted interest in fields from energy to medicine. In a nickel-hydrogen battery, the formation of poorly crystalline γ-NiOOH on the cathode has been shown to cause the memory effect of the battery (8). Titanate nanosheets have recently attracted attention in the electronics community because of their semiconducting properties (9). Hydrogen generation by aluminum-water reactions for onboard vehicular hydrogen storage (10) and the radiolytic generation of hydrogen in conjunction with metal corrosion in water in nuclear energy and waste systems (11) both involve aluminum hydroxides as reaction products. Aluminum hydroxide has also been used as a vaccine adjuvant (12) and its biochemical mode of action in a recent medical technology is being investigated (13).Boehmite is synthesized by aging noncrystalline aluminum hydroxide sol in an aqueous solution at a specific pH, and it has the basic crystal structure of double sheet of a metal-oxygen octahedron layer piled up through hydrogen bonding, as illustrated in Fig. S1. Poorly crystallized boehmite, often called pseudoboehmite (PB), forms in various crystal morphologies, such as thin films, thin platelets, and nanometer-sized rods or fibers. Importantly, the characteristics of alumina Al 2 O 3 for industrial use prepared by thermal dehydration are influenced by the morphology of the starting boehmite c...

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Performance of Several Density Functional Theory Methods on Describing Hydrogen-Bond Interactions

Cited by 135 publications

References 50 publications

A Molecular Perspective on Lithium–Ammonia Solutions

A Molecular Perspective on Lithium–Ammonia Solutions

Defining the hydrogen bond: An account (IUPAC Technical Report)

One-dimensional nanowires of pseudoboehmite (aluminum oxyhydroxide γ-AlOOH)

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