Nonequilibrium Chemical Excitation and Chemical Pumping of Lasers

Kurt E. Shuler; Tucker Carrington; John C. Light

doi:10.1364/AO.4.S1.000081

Nonequilibrium Chemical Excitation and Chemical Pumping of Lasers

Kurt E. Shuler, Tucker Carrington, and John C. Light

Applied Optics
Vol. 4,
Issue S1,
pp. 81-104
(1965)
•https://doi.org/10.1364/AO.4.S1.000081

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Kurt E. Shuler, Tucker Carrington, and John C. Light, "Nonequilibrium Chemical Excitation and Chemical Pumping of Lasers," Appl. Opt. 4, 81-104 (1965)

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Abstract

Chemical processes are reviewed which give rise to atomic or molecular products with spectroscopically observable nonequilibrium distributions among internal energy levels. Relevant theoretical considerations are reviewed, and for several types of reactions, experimental results are discussed in terms of specific examples. In several cases the existence of a population inversion seems clearly established, but it is by no means clear that the inversion density is sufficient for laser action. Certain features of molecular spectroscopy and collisional energy transfer processes bearing on the laser problem are discussed briefly.

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Reactants	Upper Laser Levels	References
Ne(Ar, Kr*) + O₂	O(3³P₂)	20, 66–68
He* + SF₆	S(4³P₂ 4p′¹F₃)	70
He* + CO₂	C(3p³D₃, 3p¹P₁, 5p¹D₂, 4d¹D₂, 6d³P₂, 4p³S₁)	70
He* + CO₂	O(3³P₂)	70
He* (Ne*) + N₂O(NO)	N(3p² S_½°, 4s⁴P_³/₂)	70
Ar* + Br₂	Br	70

Reaction		Reference	Comment
(1)	H + O₃ → OH† + O₂	90, 91	T_υ = 9,000°K, T_r = 500°K.
(1)	H + O₃ → OH† + O₂	90, 91	Partial inversion probable for $υ = 2, J ⩾ 6; υ = 1, J ⩾ 7$
(2)	H + X₂ → HX† + X	60, 89, 94–98	X = Cl, Br, F (see text)
(2)	H + X₂ → HX† + X	60, 89, 94–98	Partial inversion
(3)	H + NOCl → HCl† + NO	60, 100
(4)	H + HO₂ → OH† + OH	101, 104
(5)	O + O₃ → O₂† + O₂	29, 92, 93, 103, 104	Maximum population reported in υ = 13
(6)	O + XO₂ → O₂† + XO	99, 103, 105	X = N, Cl
(7)	O(¹D) + HX → OH† + X	105	X = H, Cl, OH, NH₂, CH₃
(8)	X + O₃ → XO† + O₂	104, 106	X = Br, Cl
(9)	N + NO → N₂† + O	107–109
(10)	X + M₂ → MX† + M	71–76	M = Na, K,Cs,…; X = Cl, Br, I
(11)	M + HgX₂ →MX† + HgXM + HgX →MX† + Hg	71–76	M = Na, K,Cs,…; X = Cl, Br, I
(12)	S + S₂Cl₂ → S₂† +SCl₂	110	$5 ⩽ υ ⩽ 12$

Reaction		Reference
(1)	M₂+X →MX+M(MX†+M→MX+M)	71–76, 82, 114	M = Na, K, CsX = Cl, Br, I	Emission from all levels of M energetically possible is observed
(2)	M + HgX → MX† + HgMX† + M → MX + M*	71–76	M = Na, K, CsX = Cl, Br, I
(3)	N + CCl → CN* + Cl	115, 124, 129, 130	(Nonthermal vibrational and rotational distributions also observed) X = Cl, H [Nonthermal vibrational excitation of excited (A³, Πg) state also reported]
(4)	C + CX → C₂* + X	115, 125, 127, 131
(5)	CO + O + M → CO₂* +M	113, 132, 133
(6)	CS₂ + O₂ → CS* + SO₂ → S₂*+ CO₂	113, 132, 133
(7)	H + Br₂ → HBr† + Br(H + HBr → H₂ + Br)	97	(²P_1/2 → ²P_3/2 of Br observed)
(8)	NO + O₃ → NO₂* + O₂	134, 135
(9)	OH† + OH† → OH* + OH	136	²Σ⁺ − ²Π
(10)	H + O₃ → OH† + O₂*	137	(¹Σ_g⁺ − ³Σ_g⁻)
(11)	O + SO → SO₂*	138
(12)	H + N₂H → NH* + NH	139	(¹Π → ¹Δ transition observed)
(13)	O + NH₃ → NH*	140	NH³Π − ³Σ ⁻
(14)	O + N₂H₄ → NH₂, OH		NH₂ (α bands)
(15)	H + N₂H₄ → NH₂, NH		OH(²Σ⁺ − ²Π), NO(²Σ⁺ − ²Π)

Reactants	Upper Laser Levels	References
Ne(Ar, Kr*) + O₂	O(3³P₂)	20, 66–68
He* + SF₆	S(4³P₂ 4p′¹F₃)	70
He* + CO₂	C(3p³D₃, 3p¹P₁, 5p¹D₂, 4d¹D₂, 6d³P₂, 4p³S₁)	70
He* + CO₂	O(3³P₂)	70
He* (Ne*) + N₂O(NO)	N(3p² S_½°, 4s⁴P_³/₂)	70
Ar* + Br₂	Br	70

Reaction		Reference	Comment
(1)	H + O₃ → OH† + O₂	90, 91	T_υ = 9,000°K, T_r = 500°K.
(1)	H + O₃ → OH† + O₂	90, 91	Partial inversion probable for $υ = 2, J ⩾ 6; υ = 1, J ⩾ 7$
(2)	H + X₂ → HX† + X	60, 89, 94–98	X = Cl, Br, F (see text)
(2)	H + X₂ → HX† + X	60, 89, 94–98	Partial inversion
(3)	H + NOCl → HCl† + NO	60, 100
(4)	H + HO₂ → OH† + OH	101, 104
(5)	O + O₃ → O₂† + O₂	29, 92, 93, 103, 104	Maximum population reported in υ = 13
(6)	O + XO₂ → O₂† + XO	99, 103, 105	X = N, Cl
(7)	O(¹D) + HX → OH† + X	105	X = H, Cl, OH, NH₂, CH₃
(8)	X + O₃ → XO† + O₂	104, 106	X = Br, Cl
(9)	N + NO → N₂† + O	107–109
(10)	X + M₂ → MX† + M	71–76	M = Na, K,Cs,…; X = Cl, Br, I
(11)	M + HgX₂ →MX† + HgXM + HgX →MX† + Hg	71–76	M = Na, K,Cs,…; X = Cl, Br, I
(12)	S + S₂Cl₂ → S₂† +SCl₂	110	$5 ⩽ υ ⩽ 12$

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