Doppler-free two-photon-excited fluorescence spectroscopy of OH in flames

J. E. M. Goldsmith; L. A. Rahn

doi:10.1364/JOSAB.5.000749

Journal of the Optical Society of America B
Vol. 5,
Issue 4,
pp. 749-755
(1988)
•https://doi.org/10.1364/JOSAB.5.000749

Doppler-free two-photon-excited fluorescence spectroscopy of OH in flames

J. E. M. Goldsmith and L. A. Rahn

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J. E. M. Goldsmith and L. A. Rahn, "Doppler-free two-photon-excited fluorescence spectroscopy of OH in flames," J. Opt. Soc. Am. B 5, 749-755 (1988)

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Abstract

High-resolution, Doppler-free fluorescence excitation spectra of OH A²Σ⁺ ← X²Π(0, 0)-band transitions were measured in low-pressure hydrogen-oxygen flames. A pulse-amplified cw dye-laser system with a 40-MHz bandwidth was used in a counterpropagating-beam geometry to excite the OH transitions by two-photon absorption. Hyperfine splittings of 15 rovibronic transitions were determined, and water-vapor pressure-broadening coefficients were measured for four of the transitions by varying the total pressure of the flame. Direct observation of the collision-broadened line shape made it unnecessary to resort to any deconvolution procedures. To our knowledge, this is the first application of a Doppler-free spectroscopic technique in a combustion environment.

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Transition	N′	J′	Centroid(cm⁻¹)		Peak-Height Ratio	Observed Splitting (MHz)	^X²Π Hyperfine Structure (MHz)^b	A²Σ⁺ HFS (MHz)

			This Work	Calculated^a				This Work	Calculated^c	Other Experiment
Q₁(1)	1	3/2	32 474.609	32 474.62	1.61	478	53.15	531	485.89	485.97 (0.16)^d
R₂(2)	3	5/2	32 455.914	32 455.92	0.68	309	−11.83	297	300.54	300.69 (0.15)^d
S₂(1)			32 516.959	32 516.97	0.63	368	−90.32	278
Q₁(3)	3	7/2	32 442.263	32 442.28	1.25	430	−7.46	423	413.95	413.71 (0.15)^d
R₁(2)			32 560.270	32 560.29	1.22	397	18.32	415
S₁(1)			32 644.192	32 644.21	1.22	386	53.15	439
Q₁(4)	4	9/2	32 424.380	32 424.39	1.08	423	−21.31	402	401.90	401.7 (2.4)^e
R₁(3)			32 577.121	32 577.13	1.31	400	−0.72	399
S₁(2)			32 695.779	32 695.79	1.30	382	14.00	396
R₁(6)	7	15/2	32 615.711	32 615.72	1.12	409	−25.31	384	384.93
S₁(5)			32 841.359	32 841.37	1.58	427	−30.92	396
R₂(10)	11	21/2	32 586.423	32 586.44	0.89	387	−38.24	349	341.75
S₂(9)			32 949.686	32 949.70	0.82	419	−78.31	341
R₁(10)	11	23/2	32 625.851	32 625.86	1.13	405	−35.91	369	376.02
S₁(9)			32 994.689	32 994.70	1.18	429	−50.40	379

Transition	This Paper	Ref. 9
Q₁(1)	1.4(0.2) × 10⁻⁴	1.7 × 10⁻⁴
S₁(5)	2.2(0.4) × 10⁻⁴	2.5 × 10⁻⁴
S₁(9)	1.6(0.3) × 10⁻⁴	1.7 × 10⁻⁴
S₂(9)	1.7(0.2) × 10⁻⁴	1.7 × 10⁻⁴

Transition	N′	J′	Centroid(cm⁻¹)		Peak-Height Ratio	Observed Splitting (MHz)	^X²Π Hyperfine Structure (MHz)^b	A²Σ⁺ HFS (MHz)

			This Work	Calculated^a				This Work	Calculated^c	Other Experiment
Q₁(1)	1	3/2	32 474.609	32 474.62	1.61	478	53.15	531	485.89	485.97 (0.16)^d
R₂(2)	3	5/2	32 455.914	32 455.92	0.68	309	−11.83	297	300.54	300.69 (0.15)^d
S₂(1)			32 516.959	32 516.97	0.63	368	−90.32	278
Q₁(3)	3	7/2	32 442.263	32 442.28	1.25	430	−7.46	423	413.95	413.71 (0.15)^d
R₁(2)			32 560.270	32 560.29	1.22	397	18.32	415
S₁(1)			32 644.192	32 644.21	1.22	386	53.15	439
Q₁(4)	4	9/2	32 424.380	32 424.39	1.08	423	−21.31	402	401.90	401.7 (2.4)^e
R₁(3)			32 577.121	32 577.13	1.31	400	−0.72	399
S₁(2)			32 695.779	32 695.79	1.30	382	14.00	396
R₁(6)	7	15/2	32 615.711	32 615.72	1.12	409	−25.31	384	384.93
S₁(5)			32 841.359	32 841.37	1.58	427	−30.92	396
R₂(10)	11	21/2	32 586.423	32 586.44	0.89	387	−38.24	349	341.75
S₂(9)			32 949.686	32 949.70	0.82	419	−78.31	341
R₁(10)	11	23/2	32 625.851	32 625.86	1.13	405	−35.91	369	376.02
S₁(9)			32 994.689	32 994.70	1.18	429	−50.40	379

Transition	This Paper	Ref. 9
Q₁(1)	1.4(0.2) × 10⁻⁴	1.7 × 10⁻⁴
S₁(5)	2.2(0.4) × 10⁻⁴	2.5 × 10⁻⁴
S₁(9)	1.6(0.3) × 10⁻⁴	1.7 × 10⁻⁴
S₂(9)	1.7(0.2) × 10⁻⁴	1.7 × 10⁻⁴

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Journal of the Optical Society of America B