Quantum mechanical investigation of N+N2 collision: state-to-state non-reaction and exchange reaction probabilities and rate constants

2021 ◽  
Author(s):  
Na Li ◽  
Hong Zhang ◽  
Xing-Lu Cheng
Keyword(s):  
Exchange Reaction ◽  
Rate Constant ◽  
Vibrational Level ◽  
Rate Constants ◽  
Low Temperatures ◽  
Vibrational Excitation ◽  
Quantum Effect ◽  
Threshold Energy ◽  
Quantum Numbers ◽  
Quantum Reaction

Abstract We present a state-to-state dynamical calculation on the exchange reaction N+N2→N2+N and the non-reaction N+N2→N+N2 based on the potential energy surface published by Mankodi et al. The calculation is performed using the time-independent quantum reaction scattering program. The reactivity of both reaction processes is discussed by reaction properties of vibrational quantum numbers v=0-3 and rotational quantum numbers j=0-32 (such as cumulative reaction probability, state-to-state reaction probabilities, and cross sections of N exchange, state-to-state rate constants for both reactions). The threshold energy of the exchange reaction can decrease with the decrease of vibrational excitation or the increase of rotational excitation. By using the J-shifting approximation, rate constants are reported for both reactions. The comparison of the presented total rate constant of the N+N2 exchange reaction with the previous results shows that the quantum effect is not negligible at low temperatures. For the exchange reaction, the rate constant at 500K decreases by about 10 orders of magnitude when the vibrational level of N2 increases from 0 to 7, indicating that the rate constants are sensitive to the initial vibrational level of N2 at low temperatures. For non-reactive collisions, the rate constants have little effect on the initial ro-vibrational levels of N2 at low temperatures.

scholarly journals Rotationally Resolved Rate Constant Measurements for Removal of CH(A2Δ and B2∑−) by Ketene

1994 ◽  
Vol 14 (4) ◽  
pp. 207-216 ◽  
Author(s):  
Jorge Luque ◽  
Javier Ruiz ◽  
Margarita Martin
Keyword(s):  
Quantum Number ◽  
Rate Constant ◽  
Cross Sections ◽  
Rate Constants ◽  
Rotational Quantum Number ◽  
Moderate Increase ◽  
Quantum Numbers ◽  
State Rate ◽  
Experimental Errors ◽  
Experimental Values

Rate constants for total removal of CH(A2Δ) and CH(B2∑−) in collisions with ketene were measured. For the A2Δ state, rate constants increased with vibrational quantum number; measured values were (4.5 ± 0.5) × 10-10 cm3 molec-1 s-1 and (8.0 ± 1) × 10-01 cm3 molec-1 s-1 for v′ = 0 and v′ = 2 respectively. For v′ = 0, rotational levels with quantum numbers from N′ = 4 to N′ = 16 were removed with similar rates within experimental errors; collisional disappearance of levels with higher rotational quantum numbers was faster for a factor of about 1.4. Calculations of cross sections for ketene and other fast colliders, assuming a multipole model, obtained a qualitative correlation with experimental values. CH(B2∑−) was more efficiently removed than CH(A2Δ, v′ = 0); for the lowest rotational levels a rate constant of (5.8 ± 0.3) × 10-10 cm3 molec-1 s-1 was measured and a moderate increase with rotational quantum number was observed.

Vibrational specificity for charge transfer versus deactivation in N2+(υ = 0, 1, 2) + Ar and O2 reactions

1994 ◽  
Vol 72 (3) ◽  
pp. 625-636 ◽  
Author(s):  
Shuji Kato ◽  
Michael J. Frost ◽  
Veronica M. Bierbaum ◽  
Stephen R. Leone
Keyword(s):  
Charge Transfer ◽  
Rate Constant ◽  
Rate Constants ◽  
Vibrational Excitation ◽  
Branching Fraction ◽  
Total Rate ◽  
Charge Transfer Rate ◽  
Transfer Channel ◽  
Selected Ion Flow Tube ◽  
Specific Reactions

Rate constants for charge transfer and vibrational deactivation in the N2+(X2Σg+, υ = 0, 1,2) + Ar and O2 reactions are directly measured by a state-resolved optical detection method. The novel, selected-ion flow tube, laser-induced fluorescence (SIFT–LIF) technique is used to study the vibrationally specific reactions at near-thermal collision energy. The total rate constant for N2+(υ = 1,2) + Ar increases by more than a factor of 40 relative to N2+(υ = 0). This enhancement is due exclusively to an increase in the charge transfer channel. The charge transfer rate constants for the N2+(υ) + Ar reaction are found to be almost identical for υ = 1 and υ = 2; this differs slightly from previous results at higher collision energies. The vibrational deactivation rate constant for the N2+(υ = 1) + Ar reaction is measured for the first time; the upper limit for the branching fraction is ≈3%, confirming that this reaction is a useful monitor for N2+(υ > 0). The total rate constant for N2+(υ = 1, 2) + O2 increases by factors of 2.6 and 3.3, respectively, relative to N2+(υ = 0). In contrast to the N2+ + Ar reaction, this enhancement is largely due to the occurrence of vibrational deactivation, which is found to be slightly faster for υ = 2 than for υ = 1. For N2+(υ = 2) + O2, the υ = 2 → 1 and υ = 2 → 0 vibrational deactivation channels are found to occur with comparable rates. The lack of substantial enhancement in the charge transfer channel in the N2+(υ) + O2 reaction by vibrational excitation (up to υ = 2) is in contrast to the observed translational enhancement, which opens a higher lying, endothermic O2+(a4Πu) product channel. These results are consistent with a short-range, curve-crossing mechanism that efficiently channels energy into the O2+(a4Πu) state.

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

The Effect of p-Toluidine on the Two-Step Electroreduction of Zn(II) in Water-Methanol and Water-Dimethylformamide

1999 ◽  
Vol 64 (4) ◽  
pp. 585-594 ◽  
Author(s):  
Barbara Marczewska
Keyword(s):  
Electron Transfer ◽  
Binary Mixtures ◽  
Rate Constant ◽  
Rate Constants ◽  
Electrode Surface ◽  
Mercury Electrode ◽  
Forward Rate ◽  
Solvent Molecules ◽  
Activated Complex

The acceleration effect of p-toluidine on the electroreduction of Zn(II) on the mercury electrode surface in binary mixtures water-methanol and water-dimethylformamide is discussed. The obtained apparent and true forward rate constants of Zn(II) reduction indicate that the rate constant of the first electron transfer increases in the presence of p-toluidine. The acceleration effect may probably be accounted for by the concept of the formation on the mercury electrode an activated complex, presumably composed of p-toluidine and solvent molecules.

Radiolysis studies on the corrosion inhibitors 1 -hexyn-3-ol, cinnamonitrile, and 1,3-diethyl-2-thiourea

1995 ◽  
Vol 73 (12) ◽  
pp. 2137-2142 ◽  
Author(s):  
A.J. Elliot ◽  
M.P. Chenier ◽  
D.C. Ouellette
Keyword(s):  
Hydrogen Atom ◽  
Hydroxyl Radical ◽  
Temperature Dependence ◽  
Rate Constant ◽  
Rate Constants ◽  
Corrosion Inhibitors ◽  
Hydrated Electron

In this publication we report: (i) the rate constants for reaction of the hydrated electron with 1-hexyn-3-ol ((8.6 ± 0.3) × 108 dm3 mol−1 s−1 at 18 °C), cinnamonitrile ((2.3 ± 0.2) × 1010 dm3 mol−1 s−1 at 20 °C), and 1,3-diethyl-2-thiourea ((3.5 ± 0.3) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile and diethylthiourea, the temperature dependence up to 200 °C and 150 °C, respectively, is also reported; (ii) the rate constants for the reaction of the hydroxyl radical with 1-hexyn-3-ol ((5.5 ± 0.5) × 109 dm3 mol−1 s−1 at 20 °C), cinnamonitrile ((9.2 ± 0.3) × 109 dm3 mol−1 s−1 at 21 °C), and diethylthiourea ((8.0 ± 0.8) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile, the temperature dependence up to 200 °C is also reported; (iii) the rate constant for the hydrogen atom reacting with 1-hexyn-3-ol ((4.3 ± 0.4) × 109 dm3 mol−1 s−1 at 20 °C). Keywords: radiolysis, corrosion inhibitors, rate constants.

Singlet Methylene Removal Rate Constants from the (0,1,0) Vibrational Level: Enhancement via Complex-Mediated Vibrational Relaxation

2001 ◽  
Vol 215 (6) ◽  
Author(s):  
M.A. Buntine ◽  
G.J. Gutsche ◽  
W.S. Staker ◽  
M.W. Heaven ◽  
K.D. King ◽  
...  
Keyword(s):  
Vibrational Level ◽  
Rate Constants ◽  
Vibrational Relaxation ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Removal Rate ◽  
Laser Flash ◽  
Laser Absorption ◽  
Photolysis Laser ◽  
Singlet Methylene

The technique of laser flash photolysis/laser absorption has been used to obtain absolute removal rate constants for singlet methylene,

An ICR mass spectrometry study of ion/molecule reactions between ethyl chloride and alkylamines

1991 ◽  
Vol 69 (2) ◽  
pp. 363-367
Author(s):  
Guoying Xu ◽  
Jan A. Herman
Keyword(s):  
Mass Spectrometry ◽  
Key Words ◽  
Rate Constant ◽  
Rate Constants ◽  
Ethyl Chloride ◽  
Ion Molecule Reactions ◽  
Mass Spectrometry Study ◽  
Ethyl Cation

Ion/molecule reactions in mixtures of ethyl chloride with C1–C4 alkylamines were studied by ICR mass spectrometry. Ethyl cation transfer to C1–C4 alkylamines proceeds mainly through diethylchloronium ions with rate constants ~3 × 10−10cm3 s−1. In the case of s-butylamine the corresponding rate constant is 0.5 × 10−10 cm3 s−1. Key words: ICR mass spectrometry, ion/molecule reactions, ethylchloride, methylamine, ethylamine, propylamines, butylamines

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