Car–Parrinello and path integral molecular dynamics study of the intramolecular hydrogen bonds in the crystals of benzoylacetone and dideuterobenzoylacetone

Durlak, Piotr; Latajka, Zdzisław

doi:10.1039/c4cp02569e

Cited by 23 publications

(26 citation statements)

References 53 publications

(97 reference statements)

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“…We note that this temperature is within the experimental range [50]. The electronic degrees of freedom were coupled by a coupling frequency of 10000 cm −1 [49], and the hydrogen mass was substituted by the deuterium mass [51,52]. A total of 20 acetylene molecules were placed in a cubic box with a length of 16Å, as depicted in FIG.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Unexpected chemistry from the homogeneous thermal decomposition of acetylene: An ab initio study

Wang

Ding

et al. 2018

Chinese Journal of Chemical Physics

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The formation of the aromatic ring during the formation of polycyclic aromatic hydrocarbons (PAHs) remains controversial and the experimental evidence is still lacking. Moreover, the formation mechanism of benzene from acetylene in the gas phase has also puzzled organic chemists for decades. Here, ab initio molecular dynamics simulations and electronic structure calculations provide compelling evidence for an unexpected competitive reaction pathway in which the aromatic ring is formed through successive additions of vinylidene. Moreover, no collisions cause bond dissociation of the acetylene molecule during the formation of benzene in this work. This study reveals the key role for the vinylidene carbene and determines the lifetime of vinylidene.

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Section: Theoretical Methodsmentioning

confidence: 99%

Unexpected chemistry from the homogeneous thermal decomposition of acetylene: An ab initio study

Wang

Ding

et al. 2018

Chinese Journal of Chemical Physics

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“…Scheme7.a) RAHB-assisted tautomerization of b-diketones; [26,40,[120][121][122][123][124][125][126][127][128][129][130][131][132][133] b) H-bond energyand chemical shift d in malondialdehyde and b-diketones; [29,115,137,138] c) H-bonde nergy in aldols; [115] d) 1,3-dicyclopropyl-2-(1,2,3-triphenylcycloprop-2-en-1-yl)propane-1,3-dione. [143] Scheme8.RAHB-assisted rearrangement of isopropenylacetate to acetylacetone.…”

Section: Reviewmentioning

confidence: 99%

“…

Resonance-assisted hydrogen bonding( RAHB), ac oncept introduced by Gilli and co-workersi n1 989, concerns ak ind of intramolecular H-bonding strengthened by ac onjugated p-system, usually in 6-, 8-, or 10-membered rings. [105][106][107] Chem.E ur.

ReviewScheme7.a) RAHB-assisted tautomerization of b-diketones; [26,40,[120][121][122][123][124][125][126][127][128][129][130][131][132][133] b) H-bond energyand chemical shift d in malondialdehyde and b-diketones; [29,115,137,138] c) H-bonde nergy in aldols; [115] d) 1,3-dicyclopropyl-2-(1,2,3-triphenylcycloprop-2-en-1-yl)propane-1,3-dione. The unique roles of RAHB in molecular rec-ognition and switches, E/Z isomeric resolution, racemization and epimerization of amino acids and chiral amino alcohols, solvatochromism, liquid-crystalline compounds, andi ns ynthons for crystal engineering and polymer materials are also discussed.

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mentioning

confidence: 99%

Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

Mahmudov

Pombeiro

2016

Chemistry A European J

136

100

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Resonance-assisted hydrogen bonding (RAHB), a concept introduced by Gilli and co-workers in 1989, concerns a kind of intramolecular H-bonding strengthened by a conjugated π-system, usually in 6-, 8-, or 10-membered rings. This Review highlights the involvement of RAHB as a driving force in the synthesis of organic, coordination, and organometallic compounds, as a handy tool in the activation of covalent bonds, and in starting moieties for synthetic transformations. The unique roles of RAHB in molecular recognition and switches, E/Z isomeric resolution, racemization and epimerization of amino acids and chiral amino alcohols, solvatochromism, liquid-crystalline compounds, and in synthons for crystal engineering and polymer materials are also discussed. The Review can provide practical guidance for synthetic chemists that are interested in exploring and further developing RAHB-assisted synthesis and design of materials.

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“…Therefore, the continuous development of theoretical quantum methods, especially molecular dynamics methods, allows accurate prediction and description of chemical mechanisms, including the mechanism of proton transfer. There have been several recent experimental and theoretical studies on PT in the solid state in molecular crystals and other solid systems like several acid crystal hydrates which have given rise to the discuss about the same nature of proton transfer mechanism, values of the barrier height of PT, about attempts to estimate the time frame of the PT phenomenon, about how the rapid movement of the proton interfaces with the slow motions of the molecular skeleton and as a consequence about nature of hydrogen bonds with existing fast proton transfer (FPT).…”

Section: Introductionmentioning

confidence: 99%

Investigations of the hydrogen bond in the crystals of tropolone and thiotropolone via car‐parrinello and path integral molecular dynamics

Durlak

Latajka

2018

J Comput Chem

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Car‐Parrinello and path integrals molecular dynamics (CPMD and PIMD) simulations were carried out for the 10π‐electron aromatic systems: 2‐hydroxy‐2,4,6‐cycloheptatrien‐1‐one, commonly known as Tropolone (I) and 2‐hydroxy‐2,4,6‐cycloheptatriene‐1‐thione, called Thiotropolone (II) in vacuo and in the solid state. The extremely fast proton transfer (FPT) and “prototropy” tautomerism in the keto‐enol (thione‐enethiol) systems have been analyzed on the basis of CPMD and PIMD methods level. Comparisons of two‐dimensional (2D) free‐energy landscapes of reaction coordinate δ‐parameter and RO…O or RO…S distances shows that the OH… tautomer to be more favorable in the Thiotropolone. The hydrogen between the oxygen and the sulfur atoms adopts a starkly asymmetrical position in the double potential well. The values of the energy barriers for the FPT were calculated and suggested a strong hydrogen bond with low barrier for FPT mechanism. These studies and the 2D average index of π‐delocalization 〈λ〉 landscape of time evolutions of RO1…O2 and RC7O2 or RC7S1 distances for the both crystals indicate that hydrogen bonds in the crystals of Tropolone (I) and Thiotropolone (II) have characteristic properties for the type of bonding model resonance‐assisted hydrogen bonds and also low‐barrier hydrogen bonds. In the crystal of the Thiotropolone (II), we found the hydrogen bond OH…S existing without the equilibrium of the two tautomers whereas in the crystal of the Tropolone (I) has been confirmed the hydrogen bond OH…O existing with the equilibrium of the two tautomers. It was also found the significant differences in frequency, speed, and the image of the FPT in the studied crystals. © 2018 Wiley Periodicals, Inc.

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Car–Parrinello and path integral molecular dynamics study of the intramolecular hydrogen bonds in the crystals of benzoylacetone and dideuterobenzoylacetone

Cited by 23 publications

References 53 publications

Unexpected chemistry from the homogeneous thermal decomposition of acetylene: An ab initio study

Unexpected chemistry from the homogeneous thermal decomposition of acetylene: An ab initio study

Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

Investigations of the hydrogen bond in the crystals of tropolone and thiotropolone via car‐parrinello and path integral molecular dynamics

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