Spectroscopic study of the reaction of active nitrogen with some organometallic compounds

1967 ◽  
Vol 45 (16) ◽  
pp. 1891-1896 ◽  
Author(s):  
R. E. March ◽  
H. I. Schiff
Keyword(s):  
Energy Transfer ◽  
Spectroscopic Study ◽  
Organometallic Compounds ◽  
Initial Energy ◽  
Emission Lines ◽  
Kcal Mole ◽  
Vibrationally Excited ◽  
Active Nitrogen ◽  
Metal Atoms

Transfer of energy from constituents in active nitrogen to gaseous organometallic compounds leads to dissociation of the organometallic and excitation of CN and (or) metal atom. Organometallic compounds of aluminium, zinc, and boron were used in this investigation. The observed emission lines from metal atoms and highly vibrationally excited CN correspond to an initial energy transfer in excess of 200 kcal/mole. The possible role of N2(5Σg+) molecules as excitors is discussed in the light of the results obtained.

THE CHEMILUMINESCENT REACTION OF ACTIVE NITROGEN WITH THALLOUS HALIDES

1963 ◽  
Vol 41 (3) ◽  
pp. 732-738 ◽  
Author(s):  
L. F. Phillips
Keyword(s):  
Energy Transfer ◽  
Light Emission ◽  
Bimolecular Reaction ◽  
Emission Lines ◽  
Kcal Mole ◽  
Third Order ◽  
Active Nitrogen ◽  
Simultaneous Production ◽  
Chemiluminescent Reaction ◽  
Overall Efficiency

Energy transfer from active nitrogen to gaseous thallous halides leads to dissociation of the halide molecules with simultaneous production of excited thallium atoms. Thallium emission lines have been observed to correspond to the transfer of up to 221 kcal/mole to the TlX molecule. The process is kinetically third order but the high overall efficiency of light emission and thallous halide destruction requires a mechanism which involves a bimolecular reaction of TlX with an excited N2 formed during N-atom recombination.

INTENSITIES OF EMISSION LINES IN FLAMES OF METAL HALIDES WITH ACTIVE NITROGEN

1963 ◽  
Vol 41 (8) ◽  
pp. 2060-2066 ◽  
Author(s):  
L. F. Phillips
Keyword(s):  
Energy Transfer ◽  
Energy Transfer Process ◽  
Nitrogen Molecule ◽  
Spectral Lines ◽  
Emission Lines ◽  
Metal Halides ◽  
Kcal Mole ◽  
Active Nitrogen ◽  
Atom Concentration ◽  
Excitation Mechanisms

The intensities of spectral lines emitted by flames of a number of metal halides with active nitrogen have been found to vary as the square of the nitrogen atom concentration. When the total energy required for simultaneous dissociation of the halide and excitation of the metal atom is less than about 200 kcal/mole the energy transfer process is too efficient to be attributed to the termolecular reaction of a halide molecule with a pair of nitrogen atoms. The observations are consistent with the hypothesis that in this case energy is transferred to the halide molecule during collision with a nitrogen molecule in the 5Σg+ state. Possible excitation mechanisms are discussed for less intense lines which would require up to 276 kcal/mole for simultaneous dissociation and excitation.

Vacuum ultraviolet chemiluminescence from the reactions of active nitrogen with I2, IBr, ICI, and ICN

1968 ◽  
Vol 46 (8) ◽  
pp. 1429-1434 ◽  
Author(s):  
L. F. Phillips
Keyword(s):  
Energy Transfer ◽  
Emission Intensity ◽  
Vacuum Ultraviolet ◽  
Nitrogen Molecule ◽  
Emission Lines ◽  
Kcal Mole ◽  
Active Nitrogen ◽  
Excitation Mechanisms ◽  
Excited Nitrogen ◽  
Cl Atoms

Numerous emission lines from excited I, Br, and Cl atoms have been observed between 1261 and 2062 Å. For the flames with I2, IBr, and ICl it is possible to assign excitation mechanisms on the basis of the dependence of emission intensity on either [N] or [N]2. In the case of dependence on [N] the emission is the result of energy transfer from an excited nitrogen molecule, which is produced by reaction of N with NI, has an energy of 185 ± 3.5 kcal/mole, and is identified with the predicted 3Δu species. The dissociation energy of NI is found to lie between 35.6 and 40 + 3.5 kcal/mole. It is proposed that excited nitrogen molecules can be produced as well as removed very rapidly by processes of the type[Formula: see text]

State-resolved collisional quenching of highly vibrationally excited pyridine by water: The role of strong electrostatic attraction in V→RT energy transfer

1999 ◽  
Vol 111 (8) ◽  
pp. 3517-3525 ◽  
Author(s):  
Michael S. Elioff ◽  
Margaret Fraelich ◽  
Rebecca L. Sansom ◽  
Amy S. Mullin
Keyword(s):  
Energy Transfer ◽  
Electrostatic Attraction ◽  
Collisional Quenching ◽  
Vibrationally Excited

THE REACTIVE COMPONENTS IN ACTIVE NITROGEN AND THE ROLE OF SPIN CONSERVATION IN ACTIVE NITROGEN REACTIONS

1956 ◽  
Vol 34 (9) ◽  
pp. 1217-1231 ◽  
Author(s):  
H. G. V. Evans ◽  
C. A. Winkler
Keyword(s):  
Experimental Information ◽  
Active Species ◽  
Convincing Evidence ◽  
Critical Examination ◽  
Vibrationally Excited ◽  
Active Nitrogen ◽  
Electronically Excited ◽  
Excited Molecules ◽  
Triatomic Radicals

Critical examination of the available experimental information provides rather convincing evidence that atomic nitrogen is the main reactive species in active nitrogen. It appears quite unlikely that a significant contribution to the activity is made by electronically excited molecules, metastable atoms, ions, or triatomic radicals. Evidence exists, however, for the presence of more than one active species, and a plausible suggestion would seem to be that the second species is vibrationally excited molecules. Consideration of the role of spin conservation in reactions of active nitrogen leads to the conclusion that reactions that conserve spin occur more readily than those in which spin is not conserved.

CN Emission in Active Nitrogen. II. The Role of Energy Transfer and Atom Transfer Reactions in CN(X2Σ+) Excitation

1972 ◽  
Vol 50 (16) ◽  
pp. 2527-2536 ◽  
Author(s):  
G. M. Provencher ◽  
D. J. McKenney
Keyword(s):  
Energy Transfer ◽  
Ground State ◽  
Absolute Intensity ◽  
Vibrationally Excited ◽  
Active Nitrogen ◽  
Band Emission ◽  
Electronically Excited ◽  
Order Of Magnitude ◽  
Three Body ◽  
A Minor

A simplified mechanism is presented for excitation of ground state CN(X2Σ+) formed from carbonaceous impurity in flowing N2 subjected to a microwave discharge. Analysis of absolute intensity data from spectrometer recordings of CN(B2Σ+ → X2Σ+) violet band emission enabled order of magnitude estimates of rate constants for CN(X2Σ+) excitation by energy transfer from vibrationally excited ground state nitrogen, [Formula: see text][Formula: see text]and formation of electronically excited NCN* in a three body reaction[Formula: see text]Energy transfer from [Formula: see text] is shown to be a minor source of excitation of CN to radiative levels. N2(A) is a source of vibrationally excited ground state nitrogen, [Formula: see text] which in turn excites CN. Vibrational population profiles under all conditions in this work are shown to be primarily a function of [Formula: see text] Evidence for the participation of the A2Π state of CN is shown in the population maxima at ν = 4 and 10 of the B2Σ+ state.

THE STUDY OF VIBRATIONALLY EXCITED N2 MOLECULES WITH THE AID OF AN ISOTHERMAL CALORIMETER

1963 ◽  
Vol 41 (4) ◽  
pp. 903-912 ◽  
Author(s):  
J. E. Morgan ◽  
H. I. Schiff
Keyword(s):  
Microwave Discharge ◽  
Reaction Vessel ◽  
Kcal Mole ◽  
Collision Efficiency ◽  
Vibrationally Excited ◽  
Active Nitrogen ◽  
First Case ◽  
Nitrogen Stream ◽  
Excited Nitrogen ◽  
Isothermal Calorimeter

Vibrationally excited nitrogen molecules produced both by a microwave discharge in nitrogen and also by the reaction[Formula: see text]have been examined using an isothermal calorimetric probe.In the first case the energy associated with an 'active' nitrogen stream, due to vibrationally excited N2, was found to be 6.03 kcal mole−1 of total nitrogen. The subsequent relaxation of this species was found to occur almost entirely on the walls of the reaction vessel, with a collision efficiency of 4.5 × 10−4. The addition of other gases greatly accelerated the homogeneous relaxation rate. Collisional efficiencies of N2O, CO2, and Ar were found to be 0.8 × l0−4, 2.3 × 10−5, and 1.0 × 10−6 respectively.The vibrationally excited nitrogen produced by the N/NO reaction was found to possess 20 ± 4 kcal mole−1 of energy compared with the maximum of 75 kcal mole−1 allowed by the exothermicity of the reaction.

Adiabatic large polarons in anisotropic molecular crystals

2011 ◽  
Vol 35 (1) ◽  
pp. 15-27
Author(s):  
Zoran Ivić ◽  
Željko Pržulj
Keyword(s):  
Energy Transfer ◽  
Effective Mass ◽  
Molecular Crystals ◽  
Single Chain ◽  
Proper Understanding ◽  
One Dimensional ◽  
Interchain Coupling ◽  
Large Polaron ◽  
The One

Adiabatic large polarons in anisotropic molecular crystals We study the large polaron whose motion is confined to a single chain in a system composed of the collection of parallel molecular chains embedded in threedimensional lattice. It is found that the interchain coupling has a significant impact on the large polaron characteristics. In particular, its radius is quite larger while its effective mass is considerably lighter than that estimated within the one-dimensional models. We believe that our findings should be taken into account for the proper understanding of the possible role of large polarons in the charge and energy transfer in quasi-one-dimensional substances.

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