An alternative gas-phase electron diffraction and quantum chemical study of nitroethane

Shishkov, Igor F.; Sipachev, V.A.; Dem’yanov, P. I.; Дорофеева, О. В.; Vogt, N.; Vishnevskiy, Yuriy V.; Vilkov, L. V.

doi:10.1016/j.molstruc.2009.11.032

Cited by 6 publications

(3 citation statements)

References 18 publications

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“…In other words, the atomic basins of two cations of M 2 X 2 intervene between two anions precluding BPA C H T U N G T R E N N U N G (X1X2) formation. [29] Similar intervention precludes a bond path formation between two oxygen atoms of NO 2 groups of CA C H T U N G T R E N N U N G (NO 2 ) 3 ion [12k] and NO 2 group of nitroethane, [30] carbon atoms in the homotropylium cation, semibullvalene, and transition state for the degenerate Cope rearrangements of semibullvalene although a relatively high delocalization of electrons between the corresponding carbon atoms does exist as it was identified by significant so called nonbonded interatomic delocalization indices. [7e] There are other examples [28e,f, 31] when contributions of extraneous atoms to ED between two particular atoms result in invalid picture of the chemical bonding predicted by the conventional QTAIM.…”

Section: S) Electron Densities At Bcpa C H T U N G T R E N N U N G (X1x2) Rcp-a C H T U N G T R E N N U N G (X1 M1x2)s and Rcpa C H T U Nmentioning

confidence: 99%

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M₂X₂(M=Li, Na, K; X=H, OH, F, Cl)

Dem’yanov

Polestshuk

2012

Chemistry A European J

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Interactions in dimers of model alkali metal derivatives M(2)X(2) (M = Li or Na or K; X = H or F, Cl, OH) are studied in the frame of the quantum theory of atoms in molecules (QTAIM) using the interacting quantum atoms approach (IQA). Contrary to opinion prevalent in QTAIM studies, the interaction between two anions linked by a bond path is demonstrated to be strongly repulsive. One may therefore say that a bond path does not necessarily indicate bonding interactions. The interactions between two anions or two cations that are not linked by a bond path are also strongly repulsive. The repulsive anion-anion and cation-cation interactions are outweighed by much stronger attractive anion-cation interactions, and the model molecules are therefore in a stable state. The attractive Ehrenfest forces (calculated in the frame of the QTAIM) acting across interatomic surfaces shared by anions in the dimers do not reflect the repulsive interactions between anions. Probable reasons of this disagreement are discussed. The force exerted on the nucleus and the electrons of a particular atom by the nucleus and the electrons of any another atom in question is proposed. It is assumed that this force unambiguously exposes whether basins of two atoms are attracted or repelled by each other in a polyatomic molecule.

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Section: S) Electron Densities At Bcpa C H T U N G T R E N N U N G (X1x2) Rcp-a C H T U N G T R E N N U N G (X1 M1x2)s and Rcpa C H T U Nmentioning

confidence: 99%

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M₂X₂(M=Li, Na, K; X=H, OH, F, Cl)

Dem’yanov

Polestshuk

2012

Chemistry A European J

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“…Clearly, Nature and quantum theory (simulating Nature) know about these trends which chemists have long tried to describe and explain with the help of a concept baptized steric'. [38] Typical examples are pairs of closed-shell atoms or molecules squeezed together by external forces, such as ions of same charge by crystal lattice interactions, or saturated H atoms by molecular crowding in biphenyl or phenanthrene, or molecules in strained inclusion complexes. [4b] However, the vast majority of chemists calls for more theory describing their 2 Among the criticisms of the chemical concepts of steric and Pauli repulsions that have appeared in the literature, the following two are mentioned.…”

Section: Conceptual Analysis Of Steric Hindrancementioning

confidence: 99%

Observations and Descriptions versus Explanations—An Example: Does Nature, Does Theory Know About Steric Hindrance?

Schwarz

Schmidbaur

2012

Chemistry A European J

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Quantum chemical investigations in the literature sometimes underpin traditional chemical concepts (such as those of different primary and secondary types of chemical bonding or of steric repulsions) but sometimes also seem to undermine them. Conceptual pitfalls in recent discussions in this and other leading journals, when combining empirically and quantum chemically based reasoning, can be avoided when taking four points into account: 1) The construction of theoretical concepts should be guided by both, physical rigor and the aim of recovering the notions that have been found chemically fruitful. 2) Partitioning of a chemical phenomenon into elementary physical steps should not only consider the stationary initial and final states but also include non-stationary intermediate states that exhibit the physically characteristic internal relaxation mechanism. 3) Even if sufficiently accurate, the partitioning into large contributions of opposite sign is less valuable for a qualitative chemical understanding, as long as the trend of one big decisive term or sum of terms cannot be made obvious (for instance on the basis of the variation principle--or by chemical intuition). 4) Causal explanatory notions, even if more vague or fuzzy than some more rigorous and unique descriptive concepts, have to be advanced towards a more fruitful chemical theory.

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“…After being emitted into the atmosphere, these compounds undergo a series of chemical reactions, leading to their removal from the troposphere or conversion into other compounds . Some experimental studies have investigated the rate coefficients of the gas-phase reactions of hydroxyl radicals with methoxyphenols and their contributions to SOA. , Theoretical calculations have also been applied to the study of the conformations and electron diffraction of some methoxyphenols in their reactions with oxidants. − …”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Reactions of Methoxyphenols with NO₃ Radicals: Kinetics, Products, and Mechanisms

et al. 2016

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Methoxyphenols, a group of important tracers for wood smoke, are emitted to the atmosphere in large quantities, but their transformations are rarely studied. In this study, the kinetics and products of the gas-phase reactions of eugenol and 4-ethylguaiacol with NO 3 radicals were investigated online using a vacuum ultraviolet photoionization gas time-of-flight mass spectrometer. The rate coefficients of the gaseous reactions of eugenol and 4-ethylguaiacol with NO 3 radicals were (1.6 ± 0.4) × 10 −13 and (1.1 ± 0.2) × 10 −12 cm 3 molecule −1 s −1 (at 298 K), indicating that the atmospheric lifetimes of the NO 3 radicals were 3.5 and 0.5 h, respectively. With the aid of gaschromatography−mass-spectrometry analysis, several types of degradation products were identified with nitro derivatives as the major products. The configurations of the nitro-product isomers and their formation mechanisms were determined via theoretical calculations. On the basis of these products, degradation pathways of the methoxyphenols with NO 3 radicals were proposed. This study determines the degradation rates and mechanisms of the methoxyphenols at night and implies the significant NO 3 nighttime chemistry.

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An alternative gas-phase electron diffraction and quantum chemical study of nitroethane

Cited by 6 publications

References 18 publications

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M₂X₂(M=Li, Na, K; X=H, OH, F, Cl)

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M₂X₂(M=Li, Na, K; X=H, OH, F, Cl)

Observations and Descriptions versus Explanations—An Example: Does Nature, Does Theory Know About Steric Hindrance?

Gas-Phase Reactions of Methoxyphenols with NO₃ Radicals: Kinetics, Products, and Mechanisms

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An alternative gas-phase electron diffraction and quantum chemical study of nitroethane

Cited by 6 publications

References 18 publications

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M2X2(M=Li, Na, K; X=H, OH, F, Cl)

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M2X2(M=Li, Na, K; X=H, OH, F, Cl)

Observations and Descriptions versus Explanations—An Example: Does Nature, Does Theory Know About Steric Hindrance?

Gas-Phase Reactions of Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms

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A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M₂X₂(M=Li, Na, K; X=H, OH, F, Cl)

A Bond Path and an Attractive Ehrenfest Force Do Not Necessarily Indicate Bonding Interactions: Case Study on M₂X₂(M=Li, Na, K; X=H, OH, F, Cl)

Gas-Phase Reactions of Methoxyphenols with NO₃ Radicals: Kinetics, Products, and Mechanisms