The photodissociation of ammonia in the absorption system. Part II. Translational excitation of the hydrogen atoms produced, and the mechanism of the predissociation

1977 ◽  
Vol 55 (8) ◽  
pp. 1387-1395 ◽  
Author(s):  
R. A. Back ◽  
S. Koda
Keyword(s):  
Isotope Effects ◽  
Quantum Yields ◽  
Translational Energy ◽  
Molecular Dissociation ◽  
Hydrogen Atoms ◽  
Bending Vibration ◽  
Upper Limits ◽  
Out Of Plane ◽  
System Part ◽  
Correlation Rules

The photolyses of NH3 and ND3 have been studied at 2139, 2062, and 1850 Å in the presence of propane and ethylene. Upper limits (none was actually observed) were established for the quantum yields of molecular dissociation of D2 from ND3 of 0.003 and 0.004 at 2139 and 2062 Å, while at 1850 Å a definite yield of 0.009 was obtained. Similar results were observed with NH3. From the dependence of hydrogen yields on the ratio of ethylene to propane, it was concluded that H and D atoms were produced in the photolysis with excess translational energy. Values of the integrated reaction probability (IRP) of hot H atoms with propane were estimated to be 0.078, 0.070, and 0.045 at 2139, 2062, and 1850 Å respectively, while corresponding values for hot D atoms from ND3 were 0.083, 0.062, and 0.029. Implications of the decrease in IRP with increasing photon energy are discussed, and it is concluded that at the shorter wavelengths a second dissociation channel leading to NH2(2A1) becomes important. A mechanism for the predissociation of the Ã-state of ammonia is presented which accounts for this behaviour and for the deuterium isotope effects observed previously. It is suggested that the dissociation does not follow the state correlation rules for dissociation in the plane of the molecule, at least when the ν2 out-of-plane bending vibration in the Ã-state is excited to levels of υ2 = 2 or higher.

Arrhenius-Parameter und kinetischer Isotopeneffekt für die Reaktion von Wasserstoffatomen mit Silan

1974 ◽  
Vol 29 (3) ◽  
pp. 493-496 ◽  
Author(s):  
Peter Potzinger ◽  
Louis C. Glasgow ◽  
Bruno Reimann
Keyword(s):  
Kinetic Isotope Effect ◽  
Relative Rate ◽  
Isotope Effects ◽  
Preexponential Factor ◽  
Kinetic Isotope Effects ◽  
Hydrogen Atoms ◽  
Kinetic Isotope ◽  
Abstraction Reaction ◽  
Upper Limits ◽  
Relative Rate Constants

The Reaction of Hydrogen Atoms with Silane; Arrhenius Parameters and Kinetic Isotope Effect Relative rate constants were measured for the systems H + C2H4/SiD4 and D + C2D4/SiH4 over a wide temperature range. From the known arrheniusparameter for the reaction H + C2H4 the activation energy EA and the preexponential factor A of the abstraction reactionH + SiD4 → HD + SiD3may be calculated. Values of EA = 3.2 kcal/Mol and A = 4.92 • 1013 cm3 Mol-1 sec-1 were obtained. Upper limits for the kinetic isotope effects are given in the paper

The photodissociation of ammonia in the absorption system. Part I. Deuterium isotope effects in the photodissociation

1977 ◽  
Vol 55 (8) ◽  
pp. 1380-1386 ◽  
Author(s):  
S. Koda ◽  
R. A. Back
Keyword(s):  
Hydrogen Atom ◽  
Isotope Effect ◽  
Isotope Effects ◽  
Quantum Yields ◽  
Absorption System ◽  
System Part ◽  
Deuterium Isotope Effects

The photolyses of mixtures of NH3, NH2D, NHD2, and ND3 have been studied at wave lengths of 2144, 2139, 2062, and 1850 Å in the presence of C3H8 as a hydrogen atom scavenger. Quantum yields of dissociation have the same values for all four species, presumably unity. Analysis of the H2 and HD produced permitted evaluation of intramolecular deuterium isotope effects in the photodissociation of NH2D and ND2H. At the two shortest wavelengths dissociation of H was favored by a factor of 2 or 3, while at 2144 and 2139 Å the isotope effect was much larger. Implications for the mechanism of the predissociation of the Ã-state of ammonia are discussed briefly. The system does not appear to be useful for the photochemical separation of deuterium.

SOME DEUTERIUM ISOTOPE EFFECTS: I. WATER SOLVOLYSIS OF METHYL-d3 ESTERS

1960 ◽  
Vol 38 (2) ◽  
pp. 222-232 ◽  
Author(s):  
J. A. Llewellyn ◽  
R. E. Robertson ◽  
J. M. W. Scott
Keyword(s):  
Isotope Effect ◽  
Isotope Effects ◽  
Zero Point ◽  
Hydrogen Atoms ◽  
Deuterium Isotope Effect ◽  
Methyl Group ◽  
Out Of Plane ◽  
Thermodynamic Effects ◽  
Inverse Isotope Effect ◽  
Activated Complex

The α-deuterium isotope effect has been examined for the solvolysis of a series of esters containing a fully deuterated methyl group. The possible sources of the effect have been divided into "thermodynamic" effects which appear to favor more rapid reaction of the protium compound and "zero point" effects where stiffening of out-of-plane vibrations may account for the direction of the observed isotope effects. It appears that the inverse isotope effect may be a measure of the spatial restrictions placed on the hydrogen atoms on the carbon atom in the activated complex.

In-Plane Vibration Modes of Arbitrarily Thick Disks

1997 ◽  
Author(s):  
Kevin I. Tzou ◽  
Jonathan A. Wickert ◽  
Adnan Akay
Keyword(s):  
Natural Frequencies ◽  
Arbitrary Dimension ◽  
Three Dimensional ◽  
Mode Shapes ◽  
Vibration Modes ◽  
Three Dimensional Model ◽  
Bending Vibration ◽  
Annular Disk ◽  
Out Of Plane ◽  
Plane Bending

Abstract The three-dimensional vibration of an arbitrarily thick annular disk is investigated for two classes of boundary conditions: all surfaces traction-free, and all free except for the clamped inner radius. These two models represent limiting cases of such common engineering components as automotive and aircraft disk brakes, for which existing models focus on out-of-plane bending vibration. For a disk of significant thickness, vibration modes in which motion occurs within the disk’s equilibrium plane can play a substantial role in setting its dynamic response. Laboratory experiments demonstrate that in-plane modes exist at frequencies comparable to those of out-of-plane bending even for thickness-to-diameter ratios as small as 10−1. The equations for three-dimensional motion are discretized through the Ritz technique, yielding natural frequencies and mode shapes for coupled axial, radial, and circumferential deformations. This treatment is applicable to “disks” of arbitrary dimension, and encompasses classical models for plates, bars, cylinders, rings, and shells. The solutions so obtained converge in the limiting cases to the values expected from the classical theories, and to ones that account for shear deformation and rotary inertia. The three-dimensional model demonstrates that for geometries within the technologically-important range, the natural frequencies of certain in- and out-of-plane modes can be close to one another, or even identically repeated.

The visible absorption spectrum of 1,2-cyclobutanedione in the gas phase

1986 ◽  
Vol 64 (11) ◽  
pp. 2152-2161 ◽  
Author(s):  
R. A. Back ◽  
J. M. Parsons
Keyword(s):  
Absorption Spectrum ◽  
Gas Phase ◽  
Singlet State ◽  
Energy Levels ◽  
Vibrational Structure ◽  
Visible Absorption Spectrum ◽  
Excited Singlet ◽  
Bending Vibration ◽  
Visible Absorption ◽  
Out Of Plane

The visible absorption spectrum of 1,2-cyclobutanedione has been measured in the gas phase at wavelengths between 4000 and 5100 Å. The absorption is attributed to the allowed π* ← n+, 1B1 ← 1A1 transition corresponding to the first excited singlet state. The spectrum shows a complex well-resolved vibrational structure which has been analysed, with some 125 bands measured and assigned. The bands at the longer wavelengths show sharp rotational fine structure, not yet analysed. The strongest band in the spectrum at 4933 Å has been assigned as the 0–0 band, while a band almost as strong at 4820 Å is attributed to excitation of one quantum of [Formula: see text], the a2 out-of-plane carbonyl bending vibration, and it is suggested that this band owes its intensity to vibronic coupling. A number of symmetric vibrations are also excited in the spectrum, but with no long progressions. Sequence bands running to the blue with an interval of about 72 cm−1 are prominent throughout the spectrum, and are assigned to v13, the a2 ring-twisting vibration. Other hot bands were also observed involving v13 which permitted estimation of energy levels for this vibration both in the ground state and the excited state. The infrared spectrum was also measured and analysed in the gas phase between 600 and 4000 cm−1, and 14 bands were assigned to fundamental vibrations; some of these assignments, at the lower frequencies, are uncertain.

Additions and corrections: Transverse compression and the secondary H/D isotope effects in intramolecular SN2 methyl-transfer reactions

1998 ◽  
Vol 76 (3) ◽  
pp. 359-370 ◽  
Author(s):  
Saul Wolfe ◽  
Chan-Kyung Kim ◽  
Kiyull Yang ◽  
Noham Weinberg ◽  
Zheng Shi
Keyword(s):  
Transition State ◽  
Isotope Effect ◽  
Isotope Effects ◽  
High Energy ◽  
Retention Mechanism ◽  
Sigmatropic Rearrangement ◽  
Orbital Theory ◽  
Bending Vibration ◽  
Kinetic Isotope ◽  
Methyl Transfer

Using ab initio molecular orbital theory mainly at the 3-21+G level, intramolecular SN2 methyl transfer between two oxygens confined within a rigid template is found to proceed exclusively by a high energy retention mechanism when the oxygens are separated by three or four bonds, and by a high energy inversion mechanism when the oxygens are separated by six bonds. Both mechanisms exist when the oxygens are separated by five bonds. The CH3/CD3 kinetic isotope effects are normal (1.21-1.34) in the retention processes and inverse (0.66-0.81) in the inversion reactions. In the case of inversion, compression of C-H bonds of the transition state by structural effects in the plane perpendicular to the O-C-O plane increases the inverse isotope effect. The retention barriers are high because retention is inherently unfavorable, even when pericyclic stabilization of the transition state is possible. The inversion barriers are high because a rigid template cannot accommodate a linear O-CH3 -O structure, and the O-C-O bending vibration is stiff (the Eschenmoser effect). Using a novel design strategy, a nonrigid template has been found in which the barrier and the CH3/CD3 kinetic isotope effect are the same as in an intermolecular reaction.Key words: Eschenmoser effect, isotope effect, compression, SN2, sigmatropic rearrangement.

scholarly journals Lyman-α photodissociation of CH3CFCl2 (HCFC-141b): Quantum yield and translational energy of hydrogen atoms

2007 ◽  
Vol 119 (4) ◽  
pp. 277-282
Author(s):  
Almuth Laeuter ◽  
Hans-Robert Volpp ◽  
Jai P. Mittal ◽  
Rajesh K. Vatsa
Keyword(s):  
Quantum Yield ◽  
Translational Energy ◽  
Hydrogen Atoms
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