G. Hancock and I. W. M. Smith, "Quenching of Infrared Chemiluminescence. 1: The Rates of De-Excitation of CO (4 ≤ v ≤ 13) by He, CO, NO, N2, O2, OCS, N2O, and CO2," Appl. Opt. 10, 1827-1842 (1971)
Infrared chemiluminescence has been observed from vibrationally excited CO, formed in the reaction, O + CS → CO + S. The quenching of the CO overtone spectrum has been studied as a function of the concentration of each of a number of added gases. A steady-state treatment is developed which allows rates to be determined for the de-excitation of individual vibrational levels of CO (4 ≤ v ≤ 13) by He, CO (v = 0), NO, N2, O2, OCS, N2O, and CO2. The experimental results are compared with theoretically predicted rates. Finally, the importance of the results for interpreting the behavior of CO vibrational lasers is considered.
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Pv,v−1 is the probability of de-exciting COv → COv−1 per collision; collision diameters have been taken from Ref. 48.
The upper entry is the rate constant, the lower Pv,v−1; 2.0 (−12) = 2.0 × 10−12.
Calculated from the rate determined for the reverse process.
Estimated from P13,12 and P12,11 for CO–O2, using the slope of the log10(P/v) vs Δν plot for CO–N2 exchange.
Table VI
Reduced Probabilities for CO–N2O and CO–CO2 V-V Exchange
v
νv,v−1
CO–N2O
CO–CO2
4
2064.0
4.0 (−4)
2.5 (−5)
5
2037.7
1.5 (−4)
1.12 (−5)
6
2011.5
7.2 (−5)
9.0 (−6)
7
1985.4
4.1 (−5)
7.3 (−6)
8
1959.3
3.3 (−5)
6.8 (−6)
9
1933.6
2.9 (−5)
7.8 (−6)
10
1907.2
2.9 (−5)
1.12 (−5)
11
1881.7
2.9 (−5)
1.6 (−5)
12
1856.1
2.5 (−5)
2.4 (−5)
13
1829.9
2.1 (−5)
2.1 (−5)
Tables (6)
Table I
Spontaneous Emission Coefficients for CO (sec−1) and Pseudo-First-Order Rate Constants for Self-quenching by Product CO (sec−1)
Av,v−1
Av,v−2
Av,v−3
kv,v−1CO[CO]
v = 1
33.4
—
—
2
64.5
0.9
—
3
92.9
2.8
0.01
4
118.0
5.6
0.05
32
5
142.0
9.3
0.12
21
6
164.3
13.9
0.26
10
7
182.0
19.0
0.45
5.5
8
200.1
25.1
0.7
2.9
9
214.1
32.0
1.1
1.8
10
227.1
39.3
1.6
1.0
11
238.8
47.7
2.3
0.7
12
248.5
56.2
3.1
0.5
13
256.3
65.6
4.1
14
262.5
75.0
5.2
Table II
Rate Constants (cm3 molecule−1 sec−1) and Values of Pv,v−1a for De-excitation of COv by He, CO, NO, O2, N2, OCS, N2O and CO
Pv,v−1 is the probability of de-exciting COv → COv−1 per collision; collision diameters have been taken from Ref. 48.
The upper entry is the rate constant, the lower Pv,v−1; 2.0 (−12) = 2.0 × 10−12.
Calculated from the rate determined for the reverse process.
Estimated from P13,12 and P12,11 for CO–O2, using the slope of the log10(P/v) vs Δν plot for CO–N2 exchange.
Table VI
Reduced Probabilities for CO–N2O and CO–CO2 V-V Exchange
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