| 1. |
- Axner, Ove, 1957-, et al.
(författare)
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Noise-immune cavity-enhanced analytical atomic spectrometry — NICE-AAS : a technique for detection of elements down to zeptogram amounts
- 2014
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Ingår i: Spectrochimica Acta Part B - Atomic Spectroscopy. - : Elsevier. - 0584-8547 .- 1873-3565. ; 100, s. 211-235
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Tidskriftsartikel (refereegranskat)abstract
- Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is a powerful technique for detection of molecular compounds in gas phase that is based on a combination of two important concepts: frequency modulation spectroscopy (FMS) for reduction of noise, and cavity enhancement, for prolongation of the interaction length between the light and the sample. Due to its unique properties, it has demonstrated unparalleled detection sensitivity when it comes to detection of molecular constituents in the gas phase. However, despite these, it has so far not been used for detection of atoms, i.e. for elemental analysis. The present work presents an assessment of the expected performance of Doppler-broadened (Db) NICE-OHMS for analytical atomic spectrometry, then referred to as noise-immune cavity-enhanced analytical atomic spectrometry (NICE-AAS). After a description of the basic principles of Db-NICE-OHMS, the modulation and detection conditions for optimum performance are identified. Based on a previous demonstrated detection sensitivity of Db-NICE-OHMS of 5×10−12 cm−1 Hz−1∕2 (corresponding to a single-pass absorbance of 7×10−11 over 10 s), the expected limits of detection (LODs) of Hg and Na by NICE-AAS are estimated. Hg is assumed to be detected in gas phase directly while Na is considered to be atomized in a graphite furnace (GF) prior to detection. It is shown that in the absence of spectral interferences, contaminated sample compartments, and optical saturation, it should be feasible to detect Hg down to 10 zg/cm3 (10 fg/m3 or 10-5 ng/m3), which corresponds to 25 atoms/cm3, and Na down to 0.5 zg (zg = zeptogram = 10-21 g), representing 50 zg/mL (parts-per-sextillion, pps, 1:1021) in liquid solution (assuming a sample of 10 µL) or solely 15 atoms injected into the GF, respectively. These LODs are several orders of magnitude lower (better) than any previous laser-based absorption technique previously has demonstrated under atmospheric pressure conditions. It is prophesied that NICE-AAS could provide such high detection sensitivity that the instrumentation should not, by itself, be the limiting factor of an assessment of elemental abundance; the accuracy of an assessment would then instead be limited by concomitant species, e.g. originating from the handling procedures of the sample or the environment.
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| 2. |
- Axner, Ove, et al.
(författare)
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Sub-Doppler dispersion and noise-immune cavity-enhanced optical heterodyne molecular spectroscopy revised
- 2008
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Ingår i: Journal of the Optical Society of America B. ; 25:7, s. 1166-1177
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Tidskriftsartikel (refereegranskat)abstract
- An expression for the peak-to-peak sub-Doppler optical phase shift of two counter-propagating modes of light, to which the noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) dispersion signal is proportional, valid for arbitrary degree of saturation, is derived. For low degrees of saturation it agrees with the expression for weakly saturating (ws) conditions, [(1+S)-1/2-(1+2S)-1/2]α0/2, where S is the degree of saturation and α0 the unsaturated peak absorption. However, the new expression, which can be written as 0.45S(1+S)-1α0/2, does not predict a distinct maximum as the ws-expression does; instead it predicts an optical phase shift that increases monotonically with S and levels off to 0.45α0/2 for large S. This alters the optimum conditions for the sub-Doppler NICE-OHMS technique and improves its shot-noise-limited detectability. The new expression is based upon the same explicit assumptions as the ws-expression but not the Kramers-Kronig’s relations, which are not valid for nonlinear responses, and is supported by experimental results up to S = 100. The new expression is expected to be valid for all techniques measuring sub-Doppler dispersion signals
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| 3. |
- Foltynowicz, Aleksandra, 1981-, et al.
(författare)
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Characterization of fiber-laser-based sub-Doppler NICE-OHMS for quantitative trace gas detection
- 2008
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Ingår i: Optics Express. - 1094-4087. ; 16:19, s. 14689-14702
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Tidskriftsartikel (refereegranskat)abstract
- The potential of fiber-laser-based sub-Doppler noise-immune cavity-enhanced optical heterodyne molecular spectrometry for trace gas detection is scrutinized. The non-linear dependence of the on-resonance sub-Doppler dispersion signal on the intracavity pressure and power is investigated and the optimum conditions with respect to these are determined. The linearity of the signal strength with concentration is demonstrated and the dynamic range of the technique is discussed. Measurements were performed on C2H2 at 1531 nm up to degrees of saturation of 100. The minimum detectable sub-Doppler optical phase shift was 5 x 10-11 cm-1 Hz-1/2, corresponding to a partial pressure of C2H2 of 1 x 10-12 atm for an intracavity pressure of 20 mTorr, and a concentration of 10 ppb at 400 mTorr.
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| 4. |
- Foltynowicz, Aleksandra, 1981-, et al.
(författare)
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Doppler-broadened noise-immune cavity-enhanced optical heterodyne molecular spectrometry signals from optically saturated transitions under low pressure conditions
- 2008
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Ingår i: Journal of the Optical Society of America. B, Optical physics. - 0740-3224 .- 1520-8540. ; 25:7, s. 1156-1165
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Tidskriftsartikel (refereegranskat)abstract
- The influence of optical saturation on noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) signals from purely Doppler-broadened transitions is investigated experimentally. It is shown that the shape and the strength of the dispersion signal are virtually unaffected by optical saturation, whereas the strength of the absorption signal decreases as (1+G+-1)-1/2, where G+-1 is the degree of saturation induced by the sideband of the frequency modulated triplet, in agreement with theoretical predictions. This implies, first of all, that Doppler-broadened NICE-OHMS is affected less by optical saturation than other cavity enhanced techniques but also that it exhibits nonlinearities in the power and pressure dependence for all detection phases except pure dispersion. A methodology for assessments of the degree of saturation and the saturation power of a transition from Doppler-broadened NICE-OHMS signals is given. The implications of optical saturation for practical trace species detection by Doppler-broadened NICE-OHMS are discussed.
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| 5. |
- Foltynowicz, Aleksandra, 1981-, et al.
(författare)
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Noise-immune cavity-enhanced optical heterodyne molecular spectrometry : Current status and future potential
- 2008
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Ingår i: Applied physics. B, Lasers and optics (Print). - Berlin / Heidelberg : Springer Berlin/Heidelberg. - 0946-2171 .- 1432-0649. ; 92:3, s. 313-326
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Tidskriftsartikel (refereegranskat)abstract
- As a result of a combination of an external cavity and modulation techniques, noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is one of the most sensitive absorption techniques, capable of reaching close-to-shot-noise sensitivities, down to 5×10-13 fractional absorption at 1 s averaging. Due to its ability to provide sub-Doppler signals from weak molecular overtone transitions, the technique was first developed for frequency standard applications. It has since then also found use in fields of molecular spectroscopy of weak overtone transitions and trace gas detection. This paper describes the principles and the unique properties of NICE-OHMS. The historical background, the contributions of various groups, as well as the performance and present status of the technique are reviewed. Recent progress is highlighted and the future potential of the technique for trace species detection is discussed.
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| 6. |
- Foltynowicz, Aleksandra, 1981-, et al.
(författare)
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Wavelength modulated noise-immune cavity-enhanced optical heterodyne molecular spectroscopy signal line shapes in the Doppler limit
- 2009
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Ingår i: Journal of the Optical Society of America. B, Optical physics. - 0740-3224 .- 1520-8540. ; 26:7, s. 1384-1394
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Tidskriftsartikel (refereegranskat)abstract
- A thorough analysis of the shape and strength of Doppler-broadened wavelength modulated noise-immune cavity-enhanced optical heterodyne molecular spectroscopy signals is presented and their dependence on modulation frequency, modulation amplitude and detection phase is investigated in detail. The conditions that maximize the on-resonance signal are identified. The analysis is based on the standard frequency modulation spectroscopy formalism and the Fourier description of wavelength modulation spectroscopy and verified by fits to experimental signals from C2H2 and CO2 measured at 1531 nm. In addition, the line strengths of two CO2 transitions in the v2→3v1+v2+v3 hot band [Pe(7) and Pe(9)] were found to differ by ~20% from those given in the HITRAN database.
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| 7. |
- Hausmaninger, Thomas, et al.
(författare)
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Depletion of the vibrational ground state of CH4 in absorption spectroscopy at 3.4 μm in N2 and air in the 1-100Torr range
- 2018
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Ingår i: Journal of Quantitative Spectroscopy and Radiative Transfer. - : PERGAMON-ELSEVIER SCIENCE LTD. - 0022-4073 .- 1879-1352. ; 205, s. 59-70
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Tidskriftsartikel (refereegranskat)abstract
- A model presented in an accompanying work predicts that mid-IR absorption signals from methane in trace concentrations in various buffer gases detected at pressures in the 1-100Torr range can be reduced and distorted due to depletion of the vibrational ground state if the molecules are exposed to laser powers in the tens of mW range or above. This work provides experimental evidence of such depletion in a resonant cavity under a variety of conditions, e.g. for intracavity laser powers up to 2W and for buffer gases of N-2 or dry air, and verifies the applicability of the model. It was found that the degree of depletion is significantly larger in N-2 than dry air, and that it increases with pressure for pressures up to around 10Torr (attributed to a decreased diffusion rate) but decreases with pressure for pressures above 20Torr (caused by an increased collisional vibrational decay rate). The maximum degree of depletion (similar to 80%) was obtained for methane in N-2 at around 15Torr. This implies that absorption spectrometry of methane can experience significant non-linear dependencies on laser power, pressure, as well as buffer gas composition. It is shown that depletion takes place also in (CH4)-C-13, which verifies the applicability of the model also for this isotopologue, and that NICE-OHMS signals detected in absorption phase are less affected by depletion than in dispersion. It was concluded that the absorption mode of detection can provide concentration assessments that are virtually free of influence of depletion for intracavity powers below 0.8 W.
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| 8. |
- Hausmaninger, Thomas, 1987-, et al.
(författare)
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Doppler-broadened NICE-OHMS beyond the cavity-limited weak absorption condition – II : experimental verification
- 2016
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Ingår i: Journal of Quantitative Spectroscopy and Radiative Transfer. - : Elsevier. - 0022-4073 .- 1879-1352. ; 168, s. 245-256
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Tidskriftsartikel (refereegranskat)abstract
- Doppler-broadened (Db) noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) is normally described by an expression, here termed the conventional (CONV) description, that is restricted to the conventional cavity-limited weak absorption condition (CCLWA), i.e. when the single pass absorbance is significantly smaller than the empty cavity losses, i.e. when α0L<<π/F. To describe NICE-OHMS signals beyond this limit two simplified extended descriptions (termed the extended locking and extended transmission description, ELET, and the extended locking and full transmission description, ELFT), which are assumed to be valid under the relaxed cavity-limited weak absorption condition (RCLWA), i.e. when α0L<π/Fα0L<π/F, and a full description (denoted FULL), presumed to be valid also when the α0L<π/Fα0L<π/F condition does not hold, have recently been derived in an accompanying work (Ma W, et al. Doppler-broadened NICE-OHMS beyond the cavity-limited weak absorption condition - I. Theoretical Description. J Quant Spectrosc Radiat Transfer, 2015, http://dx.doi.org/10.1016/j.jqsrt.2015.09.007, this issue). The present work constitutes an experimental verification and assessment of the validity of these, performed in the Doppler limit for a set of Fα0L/πFα0L/π values (up to 3.5); it is shown under which conditions the various descriptions are valid. It is concluded that for samples with Fα0L/πFα0L/π up to 0.01, all descriptions replicate the data well. It is shown that the CONV description is adequate and provides accurate assessments of the signal strength (and thereby the analyte concentration) up to Fα0L/πFα0L/π of around 0.1, while the ELET is accurate for Fα0L/πFα0L/π up to around 0.3. The ELFT description mimics the Db NICE-OHMS signal well for Fα0L/πFα0L/π up to around unity, while the FULL description is adequate for all Fα0L/πFα0L/π values investigated. Access to these descriptions both increases considerably the dynamic range of the technique and facilitates calibration using certified reference gases, which thereby significantly broadens the applicability of the Db NICE-OHMS technique.
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| 9. |
- Hausmaninger, Thomas, 1987-, et al.
(författare)
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Model for molecular absorption spectroscopy in the 1-100 Torr range in the presence of vibrational depletion - Applied to CH4 in N2 and dry air
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- When molecules whose collision induced vibrational decay rates are small are probed by molecular absorption spectroscopic (MAS) techniques the absorption signal can, under certain conditions, be reduced and distorted. The reason has been attributed to the fact that a substantial fraction of the molecules in the interaction region will reside in excited vibrational states, which leads to a depletion of the vibrational ground state. One type of molecule in which this can take place is methane. A model for this phenomenon, based on CH4 in trace concentrations in either N2 or dry air in a cylindrical gas cell, detected by mid-infrared light in the 1 - 100 Torr pressure range, is presented. Due to a fast collisional coupling between various rotational states and velocity groups we suggest that depletion in MAS can be modeled adequately by a simple three-level system to which the transport of molecules in the system is coupled as diffusion according to Fick's law, applied to each level individually. The model is verified in a separate work [Hausmaninger T et al., J Quant Spectrosc Radiat Tr. 2017;205:59-70] with good agreement. It predicts that depletion has a strong pressure dependence in the 1 - 30 Torr range, that it is significantly more pronounced in N2 than in air, and that considerable degrees of depletion can be obtained for mW powers of light (> 10% for powers > 20 mW). The findings indicate that, unless precautions are taken, depletion can adversely affect quantitative assessments performed by MAS. Means of how to reduce depletion are given.
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| 10. |
- Liu, Jianxin, et al.
(författare)
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A novel methodology to directly pre-determine the relative wavelength response of DFB laser in wavelength modulation spectroscopy
- 2019
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Ingår i: Optics Express. - : Optical Society of America. - 1094-4087. ; 27:2, s. 1249-1261
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Tidskriftsartikel (refereegranskat)abstract
- A novel methodology to directly pre-determine the relative wavelength response (RWR) of a DFB laser, in terms of a combined current linearly scanned wavelength response and current modulated wavelength response (CMWR), in wavelength modulation spectroscopy (WMS) is presented. It is shown that the assessed RWR can be used to mimic the measured response with standard deviation of discriminations that are below 3.4 x 10(-3)cm(-1) under a variety of conditions. It is also shown that its performance supersedes two commonly used assessment models of the CMWR but is slightly worse than that of the third model. however with the benefit of solely using a single fitting parameter (the concentration) instead of more. When the novel method is applied to the assessment of CO2 concentration in a Herriot-type multipass cell by using the technique of calibration-free WMS, the results show that there is virtually no difference compared to that by use of the best of the other methods. It is concluded that the novel method is more robust and simplifies the retrieval process of gas concentration.
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