Fragmentation of alkoxide ions following collisional activation. An energy-resolved study

1988 ◽  
Vol 66 (11) ◽  
pp. 2947-2953 ◽  
Author(s):  
Roger S. Mercer ◽  
Alex G. Harrison
Keyword(s):  
Kinetic Energy ◽  
Collisional Activation ◽  
Collision Energy ◽  
Relative Importance ◽  
Elimination Reaction ◽  
Proton Abstraction ◽  
Relative Stabilities ◽  
Collisionally Activated Dissociation ◽  
Reaction Channels ◽  
Alkane Elimination

The collisionally activated dissociation reactions of the C2 to C5 alkoxide ions have been studied for collisons occurring at 8 keV kinetic energy and also over the range 5 to 100 eV kinetic energy. The alkoxide ions fragment by 1,2-elimination of H2 and/or an alkane. Thus, primary alkoxide ions fragment by elimination of H2 only, secondary alkoxide ions show elimination of H2 and alkane molecules, while tertiary alkoxide ions show elimination of alkanes only. In alkane elimination, loss of CH4 is much more facilie than loss of larger alkanes. For secondary alkoxide ions, where more than one elimination reaction occurs, the energy dependence of fragmentation has been explored over the collision energy range 5 to 100 eV. The results are interpreted in terms of a step-wise mechanism involving formation of an anion-carbonyl compound ion-dipole complex, followed by proton abstraction by the H− or alkyl anion leading to the final products. The relative importance of the reaction channels is determined by the relative stabilities of these ion-dipole complexes.

scholarly journals Some Key Issues in Hypersonic Propulsion

Energies ◽  
2021 ◽  
Vol 14 (12) ◽  
pp. 3690
Author(s):  
Claudio Bruno ◽  
Antonella Ingenito
Keyword(s):  
Kinetic Energy ◽  
Constant Volume ◽  
Supersonic Combustion ◽  
Relative Importance ◽  
Friction Drag ◽  
Wave Versus ◽  
Hypersonic Propulsion ◽  
Key Issues ◽  
Drag Ratio ◽  
Critical Aspects

This paper summarizes and discusses some critical aspects of flying hypersonically. The first is the L/D (lift over drag) ratio determining thrust and that in turn depends on the slenderness Küchemann’s τ parameter. This second parameter is found to depend on the relative importance of wave versus friction drag. Ultimately, all engineering drag is argued to depend on vorticity formed at the expense of the vehicle kinetic energy, thus requiring work by thrust. Different mixing strategies are discussed and shown to depend also on mechanisms forming vorticity when the regime is compressible. Supersonic combustion is briefly analyzed and found, at sufficiently high combustor Mach, to take place locally at constant volume, unlike conventional Brayton cycles.

A collisionally activated dissociation (CAD) and computational investigation of doubly and singly charged DMSO complexes of Cu2+

2005 ◽  
Vol 83 (11) ◽  
pp. 1921-1935 ◽  
Author(s):  
John A Stone ◽  
Timothy Su ◽  
Dragic Vukomanovic
Keyword(s):  
Electron Transfer ◽  
Collision Energy ◽  
Nbo Analysis ◽  
Computational Investigation ◽  
Doubly Charged Ions ◽  
Collisionally Activated Dissociation ◽  
The Difference ◽  
Singly Charged ◽  
Doubly Charged ◽  
Charged Ions

The singly and doubly charged Cu(II)–DMSO complexes formed by electrospray have been examined by CAD and computation. The CAD spectra were obtained as a function of collision energy. The doubly charged ions, [Cu(DMSO)n]2+, were observed only for n ≥ 2. For n = 3, dissociation leads mainly to [Cu(DMSO)2]+ + DMSO+, with only a trace of [Cu(DMSO)2]2+. Although [Cu(DMSO)]2+ was never detected, computation shows that the n = 1 complex exists in a potential well. Loss of DMSO+ is computed to be exothermic for n = 1–3, the exothermicity decreasing as n increases. The singly charged complexes in the ESI spectra were [CuX(DMSO)n]+ (X = Cl, Br, NO3, HSO4, n = 1 or 2). The CAD spectra showed competition between electron transfer from anion to metal followed by loss of X and loss of DMSO+. Experiment and computation show that for [CuX(DMSO)]+, loss of X is the preferred decomposition at low collision energy. NBO analysis shows that electron transfer to Cu from DMSO decreases in [Cu(DMSO)n]2+ as n increases, the bonding becoming more electrostatic and less covalent. In [CuX(DMSO)n]+, the negative charge on X is much less than unity with most of the difference appearing on the DMSO ligand(s).Key words: copper–DMSO complexes, electrospray, CAD, structures.

Collisionally activated dissociation: Effect of collision energy and collision cell pressure

1990 ◽  
Vol 19 (2) ◽  
pp. 94-96 ◽  
Author(s):  
Horst Schweer ◽  
Gerhard Mackert ◽  
Hannsjörg W. Seyberth
Keyword(s):  
Collision Energy ◽  
Collision Cell ◽  
Collisionally Activated Dissociation

Energetics of Magnetosphere-Ionosphere system during Main Phase of Intense Geomagnetic Storms over three Solar Cycles

2018 ◽  
Vol 13 (S340) ◽  
pp. 69-70
Author(s):  
K. J. Suji ◽  
P. R. Prince
Keyword(s):  
Solar Wind ◽  
Kinetic Energy ◽  
Wind Energy ◽  
Joule Heating ◽  
Geomagnetic Storms ◽  
Main Phase ◽  
Relative Importance ◽  
Solar Cycles ◽  
Dynamo Action ◽  
Solar Wind Energy

AbstractSolar wind kinetic energy gets transferred into the Earth’s magnetosphere as a result of dynamo action between magnetosphere and solar wind. Energy is then dissipated among various dissipation channels in the MI system. In the present study, energetics of 59 intense geomagnetic storms are analyzed for the period between 1986 and 2015, which covers the three consecutive solar cycles SC 22, 23 and 24. The average solar wind energy impinging the MI system is estimated using Epsilon parameter, the coupling function. Moreover, the relative importance of different energy sinks in the MI system are quantified and is found that more than 60% of solar wind energy is dissipated in the form of ionospheric Joule heating.

scholarly journals Ringöffnung CO+- und COOCH3+·-substituierter Cyclopropane und CO-Eliminierung aus isomeren C3H5CO+-Ionen / Ring Opening of CO+ and COOCH3+· Substituted Cyclopropanes and CO Loss from Isomeric C3H5CO+ Ions

1979 ◽  
Vol 34 (3) ◽  
pp. 488-494 ◽  
Author(s):  
Helmut Schwarz ◽  
Chrysostomos Wesdemiotis
Keyword(s):  
Kinetic Energy ◽  
Energy Release ◽  
Ring Opening ◽  
Collisional Activation ◽  
Kinetic Energy Release ◽  
Ester Group ◽  
Molecular Ions ◽  
Peak Shape ◽  
Metastable Peak ◽  
Substituted Cyclopropanes

Abstract The non-decomposing molecular ions of methyl cyclopropanecarboxylate (14) are found to rearrange to ionised methyl but-3-enoate (15). For ions with sufficient internal energy to decompose, this isomerization is in competition with · OCH3 loss, via direct cleavage of the ester group. Collisional activation spectroscopy may be used to distinguish between the C3H5CO+ ions formed by · OCH3 loss from the molecular ions of 14, 15 and other isomeric precursors. Four distinct C3H5CO+ species (18-21) can be identified in this way; these C3H5CO+ ions may themselves decompose, via CO elimination. Consideration of the metastable peak shape for CO loss, in conjunction with collisional activation spectroscopy on the resulting C3H5+ -ions, leads to two main conclusions, (i) Two C3H5+ ions (22 and 27) exist in potential energy wells. The very narrow metastable peaks for CO loss from 19 and 21 (leading to 22 and 27, respectively) show that these processes are continuously endothermic. In contrast, CO loss from either 18 or 20 gives rise to much broader metastable peaks. This suggests that rate-determining rearrangement of the incipient C3H5+ cations, to a more stable isomer, occurs prior to decomposition, (ii) Elimination of CO from the [M- · OCH3]+ fragment of 14 gives rise to a composite metastable peak, thus indicating the occurrence of two competing channels for dissociation. These channels are assigned to CO loss from 18 (larger kinetic energy release) and CO loss from 19 (smaller kinetic energy release).

ChemInform Abstract: COLLISIONALLY ACTIVATED DISSOCIATION OF HIGH KINETIC ENERGY IONS

1984 ◽  
Vol 15 (40) ◽  
Author(s):  
P. J. TODD ◽  
F. W. MCLAFFERTY
Keyword(s):  
Kinetic Energy ◽  
Collisionally Activated Dissociation ◽  
High Kinetic Energy
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