The authors gratefully acknowledge the financial support provided by the S&#234;r Cymru National Research Network in Advanced Engineering and Materials (NRN073) and Innovate UK via the Aerospace Technology Institute (113037).

1. Selecting Wavelength Range
<ol>
	<li>The wavelength range of the lightning to be observed must first be selected. 450 nm to 890 nm was selected. 
	NOTE: This will be limited by the laboratory setup, the spectral range as defined by the blazing angle of the grating, and the sensitivity of the camera.</li>
</ol>
2. Preparing the Electrodes
<ol>
	<li>Choose a suitable electrode material. A pair of 60 mm diameter hemispherical tungsten electrodes fixed to copper mountings was chosen, as illustrated in Figure 5. 
	&#8203;NOTE: Any material with which the lightning arc interacts will emit a spectrum, including the electrode, and it is important to minimize this interference. However, this should be balanced against the ability of the electrode material to withstand repeated lightning strikes with minimal damage during experimentation. For tungsten, many of its emission lines within the chosen wavelength range are only visible between 450 nm and 590 nm and are largely distinguishable from an expected lightning spectra. It is also a very hard material that is commonly used in high voltage and high current experimentation.</li>
	<li>Clean and polish the electrodes to remove any contaminants. Any material with which the lightning arc interacts will emit a spectrum, including that of any contaminants. It is, therefore, important to ensure that the electrodes are contaminant free to ensure no erroneous spectral lines.
	<ol>
		<li>Rub the electrode with coarse sandpaper for 5 min, place it into a sonic water bath at room temperature for 10 min, then wipe with a lint free cloth to loosen and remove any contaminants. Always use gloves when handling the electrode to avoid recontamination.</li>
		<li>Repeat the above typically ten to fifteen times with decreasing grades of sandpaper, emery cloth, and then polishing cloths until a good polish finish is achieved. Sandpaper and cloth grades of 240 to 8,000 were used.</li>
	</ol>
	</li>
	<li>Mount the electrodes within the lightning rig establishing a suitable distance between them. Here, the electrodes are mounted within the lightning rig 14 mm apart as shown in Figure 5. 
	NOTE: Different lightning test facilities have different operational voltages, so the distance between the electrodes should be such that an air breakdown will occur when the lightning impulse generator is triggered.</li>
</ol>
3. Preparing the Spectrograph
<ol>
	<li>Place the spectrograph in an independent EMI rated enclosure, as illustrated in Figure 2. Ideally, the lightning rig and spectrograph should be housed in separate EMI enclosures.</li>
	<li>Select and install the fiber optic. The chosen fiber was an 8 m long fiber optic and installed between the two EMI chambers.
	<ol>
		<li>Chose a fiber optic with good transmission properties within the predefined wavelength range to be observed, i.e., between 450 nm to 890 nm.</li>
		<li>Note the transmission efficiency against wavelength data as this will be used for data post-processing. This is often provided by the manufacturer although, ideally, it should be measured using a calibrated lamp.</li>
		<li>Connect one end of the fiber optic to the optic chassis in a light-tight arrangement.</li>
		<li>Position the other end of the fiber optic to view the lightning arc between the electrodes. Light from a laser sent through the spectrometer in reverse can help with alignment. The fiber optic is positioned at the same height as the center of the electrode gap at 2 m, as shown in Figure 6.</li>
		<li>Adjust the amount of light reaching the camera if necessary to minimize any saturation. A collimator is used which reduces the fiber optic viewing angle to 0.12&#176; resulting in a spot size of 4.2 mm at the position of the lightning arc for a total arc length of 14 mm, reducing the light by approximately one quarter. 
		NOTE: The intensity of light reaching the camera can alternatively be adjusted by altering the distance between the light source and fiber optic, by adjusting the slit, or by using a neutral density filter.</li>
	</ol>
	</li>
	<li>Switch the spectrograph system on and start the associated control software. The digital camera requires around 10 min to reach a temperature of -70 &#176;C. 
	NOTE: Some digital cameras require cooling to reduce noise before they become fully operational.</li>
	<li>Select the spectrograph grating. A 900 ln/mm 550 blaze grating was used. 
	&#8203;NOTE: The grating defines the wavelength range and spectral resolution within the spectrograph system used, with a spectral resolution of &#60;1 nm required for peak identification. The selected grating gives a wavelength range of approximately 140 nm and a resolution of 0.6 nm.</li>
	<li>Calibrate the spectrograph against a known calibration source, such as a Mercury-Argon lamp.
	<ol>
		<li>Position the grating in its starting position at the bottom of the preselected wavelength range. Here, the grating was positioned at 450 nm giving a range of 450 nm to 590 nm.</li>
		<li>Switch the calibration source on and place it against the open end of the fiber optic.</li>
		<li>Adjust the camera exposure via the control software to a suitable time to achieve a good unsaturated signal, such as an exposure of 0.1 s.</li>
		<li>Adjust the slit via the control software to sharpen the spectral peaks if required or, in some cases, the position of the detector can also be adjusted to optimize the signal. A slit of 100 &#181;m was used. 
		NOTE: The slit should be set to a minimal value to decrease the broadening of the atomic lines due to diffraction of light at the slit, with values up to 20 &#181;m often used. However, a narrow slit will also reduce the signal and a balance may need to be found between light intensity and sharpness of peaks.</li>
		<li>Record the spectra of the calibration source and identify the pixel number on the resulting camera image at which the peaks occur.</li>
		<li>Plot the position of the pixel number for each peak against the known wavelength of each peak provided with the calibration source and fit a straight line to derive an equation which will allow the conversion of pixels to wavelength. An example of this for three known Mercury atomic lines is illustrated in Figure 7.</li>
		<li>Apply the calibration to this grating position before moving onto the next. For some spectrograph systems, the conversion of pixel number to wavelength can be applied to the software using a calibration file.</li>
		<li>Position the grating for the next subrange and repeat the above steps. Here, the grating was next positioned to 550 nm giving a range of 550 nm to 690 nm resulting in an overlap of 40nm with the previous wavelength range. 
		NOTE: The width of the overlap region needs to be sufficient to allow the recognition of trends at the end of the first range and beginning of the second range for the later step and glue process.</li>
		<li>Repeat the above steps for all grating positions. This was repeated until 890 nm was reached. 
		NOTE: Calibration sources, typically a lamp with known spectral peaks, are usually provided with spectrograph systems and the manufacturer will be able to provide more details on how calibration can be achieved.</li>
	</ol>
	</li>
	<li>Select spectrograph parameters to record the generated lightning arc.
	<ol>
		<li>Adjust the slit further if required.</li>
		<li>Set the camera exposure time to ensure that the entire lightning event is captured; consider the trigger time and any delays in any in either the lightning generator or spectrograph when setting this parameter. For the lightning generator at MBLL, an exposure time of 5 s was used. 
		NOTE: A longer exposure time will increase noise levels and the likelihood of artifacts, such as cosmic rays, so efforts should be made to keep this to a minimum. However, the time must also be sufficient to account for any uncertainty in the triggering of the generated lightning arc or spectrograph system to ensure the entire event is captured.</li>
		<li>Change the spectrograph system mode to receive a trigger from the lightning generator. A 5 V TTL signal was used to trigger the camera 2.5 s before the lightning arc was initiated.</li>
	</ol>
	</li>
</ol>
4. Running an Experiment
<ol>
	<li>Prepare the lightning generator.
	<ol>
		<li>Ensure that all lights are off and chambers are closed where relevant to ensure a light-tight environment.</li>
		<li>Switch on the lightning generator. Each lightning test facility will have its own protocol for preparing and switching on. At MBLL, the area is cleared of personnel and the relevant safety devices are engaged before the lightning generator can be activated.</li>
		<li>Select the relevant lightning waveform and charge to the required peak current. A typical 54 kV, 100 kA peak critically damped oscillatory 100 &#181;s peak 18/40 &#181;s waveform was used.</li>
	</ol>
	</li>
	<li>Acquire spectra from multiple generated lightning events
	<ol>
		<li>Position the spectrograph grating at its start position and take a background image using the same parameters as for the lightning strike. This may be an average of several background images. A 5 s exposure with a 100 &#181;m slit was used at the 450 nm setting.</li>
		<li>Ensure the spectrograph system is ready to be triggered to record the spectra with the correct settings. A 5 s exposure with a 100 &#181;m slit was used at the 450 nm setting.</li>
		<li>Charge the lightning generator and trigger the lightning event, which will also trigger the spectrograph.</li>
		<li>Record the output spectral data.</li>
		<li>Check the spectroscopic data for any interference. Spectrographs are occasionally prone to data spikes caused by cosmic radiation or other artifacts caused by non-responsive or dead pixels. Efforts should be made to remove such interference and some spectrographs have software which can do this. An alternative is to disregard the data and repeat the experiment. Figure 8 shows an example of the difference between data with and without a cosmic radiation spike.</li>
		<li>Clean the electrodes of any contamination if required by either wiping down with alcohol or, if contaminated, repeating step 2.2.</li>
		<li>Repeat steps 4.2.2 to 4.2.5 until four sets of spectroscopic data for the 450 nm range have been achieved.</li>
		<li>Position the spectrograph grating to 550 nm and repeat steps 4.2.1 to 4.2.6 until four sets of spectrograph data for the 550 nm range have been achieved. 
		NOTE: The number of repeated steps needs to be sufficient to average out any shot-to-shot variance seen in the generated lightning arc.</li>
		<li>Repeat the above until all datasets have been collected to reach the maximum wavelength value of 890 nm, resulting in sixteen sets of spectral data.</li>
		<li>If there is significant variation in the spectra of each subrange at the same lightning current generator settings, for example, in the intensity of atomic lines, then the experiments at each stage may have to be repeated more than four times. The purpose of this is to minimize the effect of any one-off anomalies and to average out the shot-to-shot variation from the lightning generator and the lightning free arc.</li>
		<li>If there is a difference in spectra at the same lightning current generator settings, then the experimental setup may need to be assessed for contaminants.</li>
	</ol>
	</li>
</ol>
5. Post-processing Data
<ol>
	<li>For the post-processing and analysis of data, select a spreadsheet software application incorporating calculation capabilities. Such software is widely available.</li>
	<li>Subtract the background data acquired in step 4.2.1 from each relevant generated lightning spectra data.
	<ol>
		<li>The average of the 450 nm background data is subtracted from each 450 nm generated spectra data, the average of the 550 nm data is subtracted from each 550 nm generated lightning spectra data, and so on. An example of this is shown in Figure 9.</li>
	</ol>
	</li>
	<li>Average each individual set of data for each wavelength range. This is illustrated in Figure 10 where the four 450 nm datasets are averaged.</li>
	<li>Use the overlapping region to align consecutive spectra data, then average the overlapping region. This is illustrated in Figure 11 which shows the averaged 450 nm and 550 nm data. 
	NOTE: The alignment and averaging of the overlapping region will introduce errors and it may be necessary to carry out a relative intensity calibration for the complete spectrum using, for example, a tungsten ribbon lamp.</li>
	<li>Correct for fiber optic attenuation and quantum efficiency. This is illustrated in Figure 12. 
	NOTE: A more accurate correction can be achieved by using a calibrated lamp to measure the transmission of light for each subrange. In this case, the correction can be applied before the stitching process.</li>
	<li>Present the final data as either a graphical representation or an intensity plot, as shown in Figure 13.</li>
</ol>
6. Analyzing Data
<ol>
	<li>Identify the characteristic spectral peaks.
	<ol>
		<li>Some spectrograph systems will include software which will automatically identify element peaks. Care should be taken, especially with stitched data, that the peak locations are correct.</li>
		<li>Manual peak identification can be done using publicly available databases, such as24. Care should be taken to fit the strongest (relative intensity) peaks from the lowest ionization levels first (i.e., I, then II, then III) one element at a time.</li>
		<li>Problems in accurately identifying peaks or aligning them may be due to calibration issues or misalignments in the optics. Assess the position of the optics in the optics chassis and repeat step 3. 
		NOTE: The high energy of the generated lightning arcs will cause broadening of the atomic emission lines due to the Stark Effect and reliable identification of all lines may not be possible.</li>
	</ol>
	</li>
</ol>

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<li>Orville, R. E. <a target="_blank" href="http://adsabs.harvard.edu/abs/1968JAtS...25..839O">A high-speed time-resolved spectroscopic study of the lighting return stroke.</a> J. Atmos. Sci. 25, 827-856 (1968).</li>
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<li>Orville, R., Henderson, R. <a target="_blank" href="http://journals.ametsoc.org/doi/abs/10.1175/1520-0469(1984)041%3C3180%3AASIMOL%3E2.0.CO%3B2">Absolute spectral irradiance measurements of lightning from 375 to 880 nm.</a> J. Atmos. Sci. 41 (21), 3180-3187 (1984).</li>
<li>Warner, T. A., Orville, R. E., Marsh, J. L., Huggins, K. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1029/2011JD015663/abstract">Spectral (600-1050 nm) time exposures (99.6 µs) of a lightning stepped leader.</a> J. Geophys. Res. 116, 12210(2011).</li>
<li>Zhao, J., Yuan, P., Cen, J., Liu, J., Wang, J., Zhang, G. <a target="_blank" href="http://aip.scitation.org/doi/abs/10.1063/1.4827182?journalCode=jap">Characteristics and applications of near-infrared emissions from lightning.</a> J. of Appl. Phys. 114, 163303(2013).</li>
<li>Walker, T. D., Christian, H. J. <a target="_blank" href="http://www.nssl.noaa.gov/users/mansell/icae2014/preprints/Walker_292.pdf">Novel observations in lightning spectroscopy.</a> XV International Conference on Atmospheric Electricity. , USA. (2014).</li>
<li>Cen, J., Yuan, P. <a target="_blank" href="http://www.sciencedirect.com/science/article/pii/S0169809515001362">Spectral characteristics of lightning dart leader propagating in long path.</a> Atmos. Res. 164-165, 95-98 (2015).</li>
<li>Xue, S., Yuan, P., Cen, J., Wang, X. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1002/2014JD022598/full">Spectral observations of a natural bipolar cloud-to-ground lightning.</a> J. Geophys. Res.: Atmos. 120, 1972-1979 (2015).</li>
<li>Sousa Martins, R., Zaepffel, C., Chemartin, L., Lalande, P. h, Soutiani, A. <a target="_blank" href="http://iopscience.iop.org/article/10.1088/0022-3727/49/41/415205/meta">Characterization of a high current pulsed arc using optical emission spectroscopy.</a> J. of Phys. D: Appl. Phys. 49, 415205(2016).</li>
<li>Mitchard, D., Clark, D., Carr, D., Haddad, A. <a target="_blank" href="http://aip.scitation.org/doi/full/10.1063/1.4962205">Techniques for the comparison of light spectra from natural and laboratory generated lightning current arcs.</a> Appl. Phys. Lett. 109, 093502(2016).</li>
<li>Uman, M. A. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1029/JB074i004p00949/abstract">Determination of lightning temperature.</a> J. Geophys. Res. 74 (4), 949-957 (1969).</li>
<li>Prueitt, L. M. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1029/JZ068i003p00803/abstract">The excitation temperature of lightning.</a> J. Geophys. Res. 68, 803-811 (1963).</li>
<li>Uman, M. A. <a target="_blank" href="http://ieeexplore.ieee.org/document/5217654/?reload=true">Quantitative lightning spectroscopy.</a> IEEE Spectrum. 3, 102-110 (1966).</li>
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<li>Stone, C., Simpson, H., Leichauer,, Griffiths, H., Haddad, A., Cole, M., Evans, S. Establishment of a lightning test laboratory for direct-effects research. International Conference on Lightning and Static Electricity. , USA. (2013).</li>
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The authors have nothing to disclose.

Spectroscopy is a useful tool for identifying chemical element reactions during both natural and generated lightning strikes. Given a sufficiently accurate and reproducible experimental setup, further analysis on the data can reveal a variety of other lightning properties. It has, for example, been used to verify that the spectra of laboratory generated lightning arcs are spectrally similar to natural lightning and that the addition of other materials into the lightning arc can alter this spectrum significantly14. The method can also be used for other light emitting events such as fast electrical discharges, partial discharges, sparking, and other related phenomena in high voltage systems, where the simultaneous identification of multiple atomic lines or elements across a broad spectrum is important.
The most critical step is to ensure the correct parameters are used when setting up the spectrograph, such as the slit, grating, and camera settings, to acquire the best data possible resulting in strong, sharp spectral peaks. Efforts should be made to also ensure that the detector is not saturated when optimizing the signal. The position of the fiber can also be adjusted and/or collimated to improve light intensity, as well as ensuring that any stray light not part of the lightning event is either eliminated or removed as part of the background imaging process. This may take some trial and error. The ability of the lightning generator used to reproduce the same lightning event accurately with minimal variation, or to understand where any variations may come from so that they can be controlled, is important in obtaining reliable and repeatable spectroscopic results.
Alterations can be made to this setup to assess different parts of the electromagnetic spectrum further into the UV and IR bands where imaging technology allows and depending on the type of event being imaged. For example, extending the wavelength range below 450 nm can reveal further atomic and molecular lines, such as emissions from NO and OH radicals. Adjusting the spectrograph grating to give a lower resolution over a broader range may help to identify interesting features, which can then be analyzed using a higher resolution narrower range grating.
The main advantage of this technique is that it is entirely non-intrusive, so it does not require any alteration to the lightning generator. By transporting the light via a fiber optic, the amount of electrical interference from the harsh electromagnetic environment is reduced, which other systems, such as cameras, may experience if not sufficiently shielded. This means that the data from a spectrograph potentially have much lower noise and less interference than other instruments. This specific technique is limited by its lack of time resolution and subsequent lack of further characterization of the lightning arc. For example, high-speed spectrographs do exist which can produce time resolved spectral data leading to temperature and electron density measurements. 
It is expected that spectroscopy will become an important tool, alongside other diagnostic instrumentation, in understanding laboratory generated lightning arcs. It will contribute complimentary information on characteristic lightning event signatures and be used to identify the reactive chemical elements within the arc. Further development of this technique may also result in the derivation of additional characteristics.

Lightning is one of the most common and destructive forces in nature characterized by a rapid electrical discharge seen as a flash of light and followed by thunder. A typical lightning arc can consist of a voltage of tens of gigavolt and an average current of 30 kA across an arc tens to hundreds of kilometers long all happening within 100 &#181;s. Observation of the light emission spectrum from lightning events have long been used to derive information about their properties. Many techniques were established using traditional film-based camera techniques for the study of natural lightning strikes during the 1960s to 1980s, for example1,2,3,4,5,6,7and, more recently, modern digital techniques, for example8,9,10,11,12,13,14, have been used to give a more accurate insight into lightning mechanisms. Over time, such work has demonstrated the ability to not only identify chemical element interactions1,14, but also obtain measurements of temperature15,16, pressure5, particle and electron density5,17, energy18, resistance, and internal electric field of the arc8. However, studies of natural lightning have always been limited by the inherently unpredictable random and non-repeatable nature of lightning events.
In recent years, research has focused on how lightning interacts with the surrounding environment, notably in the aerospace industry to protect aircraft in flight from direct lightning strikes. Several large lightning test facilities have consequently been designed and built to replicate the most destructive elements of a lightning strike, namely the current and delivery time, but at a limited voltage. The Morgan-Botti Lightning Laboratory (MBLL)19 at Cardiff University can generate four distinct lightning waveforms up to a 200 kA in accordance to the relevant standard20. With such a laboratory facility, lightning can be easily reproduced and controlled with a high degree of accuracy and repeatability, providing a test bed for the development of new sensors and diagnostic techniques to understand lightning interactions and mechanisms better21,22,23. One such technique is a recently developed and installed spectroscopic system14,21 which, like the spectroscopic systems used in natural lightning studies, operates in the Ultraviolet (UV) to Near-Infrared (NIR) range. It is a non-intrusive method which does not interfere with the lightning arc and is largely unaffected by the electromagnetic noise produced during a strike, unlike most electronically based devices.
The spectrograph system was used to observe the spectrum of a typical laboratory generated lightning arc consisting of a 100 kA peak critically damped oscillatory, 100 &#181;s duration, 18/40 &#181;s waveform across an air gap between a pair of 60 mm diameter tungsten electrodes separated by a 14 mm air gap. A typical trace of this lightning arc waveform is shown in Figure 1. The electrodes were positioned in an Electromagnetic Impulse (EMI) light-tight chamber so that the only recorded light was from the lightning arc itself, with a small amount of this light being transported via a 100 &#181;m diameter fiber optic, positioned 2 m away and collimated to a 0.12&#176; viewing angle giving a spot size of 4.2 mm at the position of the arc, to another EMI chamber containing the spectrograph system, as shown in Figure 2. The EMI chambers were used to minimize the adverse effects caused by the lightning event. The fiber optic is terminated at the light-tight optic chassis based on a Czerny-Turner configuration of focal length 30 cm, with the light passing through an adjustable 100 &#181;m slit and onto a 900 ln/mm 550 blaze rotatable grating via three mirrors, onto a 1,024 x 1,024 pixel digital camera, as shown in Figure 3. In this case, the optical setup gives a spectral resolution of 0.6 nm across an approximately 140 nm subrange within an approximate full range of 800 nm across UV to NIR wavelengths. The spectral resolution is measured as the ability of the spectrograph to distinguish two close peaks, and the position of the subrange within the full range can be adjusted by rotating the grating. A key component of the system is the choice of diffraction grating which dictates the wavelength range and the spectral resolution, with the former being inversely proportional to the latter. Typically, a broad wavelength range is needed to locate multiple atomic lines whereas a high spectral resolution is needed to measure their position accurately; this cannot be physically achieved with a single grating for this type of spectrograph. Therefore, data from several subranges, with high resolution, are taken at various positions across the UV to NIR range. These data are stepped and glued together to form a composite spectrum.
In practice, due to limitations in the fiber optic light transmission, a spectrum wavelength range of 450 nm to 890 nm was recorded. Starting at 450 nm, light from four independent generated lightning arcs was recorded, background noise was subtracted, and they were then averaged. The wavelength range was then shifted to 550 nm, giving a 40 nm data overlap, with light from another four generated lightning arcs recorded and averaged. This was repeated until 890 nm was reached, and the resulting averaged data were stitched together to create a complete spectrum across the full predefined wavelength range. This process is illustrated in Figure 4. Characteristic peaks were then used to identify chemical elements through comparison to an established database24.
In this paper, the method of optical emission spectroscopy is described. This method is readily applicable to a wide range of other light emitting events with minimal alteration to the experimental setup or spectrograph system settings. Such applications include fast electrical discharges, partial discharges, sparking, and other related phenomena in electrical systems and equipment.

<table><tbody><tr><td>Lightning Generator, including EMI shielded chambers, lightning rig and associated control and safety systems</td><td>Cardiff University</td><td>N/A</td><td>Designed, developed and constructed by Cardiff University</td></tr><tr><td>60mm diameter tungsten electrodes with copper mountings</td><td>Unknown</td><td>N/A</td><td>Available from any specialist electrode / high voltage equipment manufacturer</td></tr><tr><td>Spectrograph, including chassis, camera, optic fibre and control software</td><td>Andor</td><td>Chassis: SR-303i-B-SIL</td><td></td></tr><tr><td></td><td></td><td>Camera: DU420A-BU2</td><td></td></tr><tr><td></td><td></td><td>Optic Fibre: 249309 SR-OPT-8018-9RX</td><td></td></tr><tr><td></td><td></td><td>Software: Solis v4.25</td><td></td></tr><tr><td>Mercury argon calibration source</td><td>Ocean Optics</td><td>HG-1</td><td></td></tr><tr><td>Anaylsis software</td><td>Microsoft</td><td>Excel 2016</td><td></td></tr></tbody></table>

method for recording broadband high resolution emission spectra of laboratory lightning arcs

Lightning is one of the most common and destructive forces in nature and has long been studied using spectroscopic techniques, first with traditional camera film methods and then digital camera technology, from which several important characteristics have been derived. However, such work has always been limited due to the inherently random and non-repeatable nature of natural lightning events in the field. Recent developments in lightning test facilities now allow the reproducible generation of lightning arcs within controlled laboratory environments, providing a test bed for the development of new sensors and diagnostic techniques to understand lightning mechanisms better. One such technique is a spectroscopic system using digital camera technology capable of identifying the chemical elements with which the lightning arc interacts, with these data then being used to derive further characteristics. In this paper, the spectroscopic system is used to obtain the emission spectrum from a 100 kA peak, 100 &#181;s duration lightning arc generated across a pair of hemispherical tungsten electrodes separated by a small air gap. To maintain a spectral resolution of less than 1 nm, several individual spectra were recorded across discrete wavelength ranges, averaged, stitched, and corrected to produce a final composite spectrum in the 450 nm (blue light) to 890 nm (near infrared light) range. Characteristic peaks within the data were then compared to an established publicly available database to identify the chemical element interactions. This method is readily applicable to a variety of other light emitting events, such as fast electrical discharges, partial discharges, and sparking in electrical equipment, apparatus, and systems.

A representative lightning intensity against wavelength plot for a 100 kA peak critically damped oscillatory 100 &#181;s peak 18/40 &#181;s waveform, across an air gap between a pair of 60 mm diameter tungsten electrodes positioned 14 mm apart, is given in Figure 14. These data consist of four sets of four 140 nm averaged data segments stitched together and corrected for background noise, fiber optic attenuation, and the digital camera quantum efficiency. These data have been converted into an intensity plot, as shown in Figure 15. Prominent peaks have been manually identified through comparison to an established database, as shown in Figure 16.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56336/56336fig1.jpg" /> 
Figure 1: Generated lightning arc profile. The recorded trace of a typical 100 kA peak critically damped oscillatory, 100 &#181;s duration, 18/40 &#181;s generated lightning waveform. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56336/56336fig2.jpg" /> 
Figure 2: Experimental setup. A schematic of the experimental setup (not to scale), where light from a generated lightning arc between two electrodes is transported via a fiber optic to the spectroscopic system, consisting of an optics chassis and digital camera. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56336/56336fig3.jpg" /> 
Figure 3: Spectrograph setup. A schematic of the spectrograph system (not to scale), where light from the fiber optic is turned into a spectrum, via a grating, which is then recorded by a digital camera. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig3large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56336/56336fig4.jpg" /> 
Figure 4: Collating, processing, and presenting spectral data. An illustration of the steps used to collate, average, stitch, and correct data towards achieving a broad high resolution spectrum. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig4large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56336/56336fig5.jpg" /> 
Figure 5: Electrode configuration. An image of the two 6 mm diameter hemispherical tungsten electrodes fixed to copper mountings positioned 14 mm apart within the lightning rig. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig5large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56336/56336fig6.jpg" /> 
Figure 6: Fiber optic configuration. An image of the fiber optic positioned at the same height and at a distance of 2 m from the mounted electrodes. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig6large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56336/56336fig7.jpg" /> 
Figure 7: Wavelength calibration. (a) A table of three known Mercury lines against the pixel number at which they were measured, and (b) a plot of each point (crosses) and a straight-line fit (dashed line) giving an equation (inset) allowing pixels to be converted to wavelength. This is done for multiple known atomic lines across the entire wavelength range. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig7large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/56336/56336fig8.jpg" /> 
Figure 8: Cosmic ray interference. Spectral data from a 100 kA laboratory generated lightning arc in the 550 nm to 690 nm range showing: (a) data with no cosmic ray interference, and (b) and (c) data with characteristic cosmic ray spikes. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig8large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 9" class="xfigimg" src="/files/ftp_upload/56336/56336fig9.jpg" /> 
Figure 9: Subtraction of background. Spectral data from a 100 kA laboratory generated lightning arc in the 550 nm to 690 nm range showing: (a) averaged background data, (b) raw data, and (c) data with average background subtracted. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig9large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 10" class="xfigimg" src="/files/ftp_upload/56336/56336fig10.jpg" /> 
Figure 10: Averaging data. Spectral data from a 100 kA laboratory generated lightning arc in the 550 nm to 690 nm range showing: (a-d) individual data, and (e) averaged data. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig10large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 11" class="xfigimg" src="/files/ftp_upload/56336/56336fig11.jpg" /> 
Figure 11: Stitching data. Spectral data from a 100 kA laboratory generated lightning arc showing: (a) the 550 nm to 690 nm range, (b) the 650 to 790 nm range, and (c) the two overlaid datasets with a 650 nm to 690 nm overlap. The overlap region is then averaged. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig11large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 12" class="xfigimg" src="/files/ftp_upload/56336/56336fig12.jpg" /> 
Figure 12: Correcting data. Plots in the 450 nm to 890 nm wavelength range for (a) fiber attenuation, and (b) spectrograph camera quantum efficiency provided by respective manufacturers. These are used to correct the stitched spectral data accordingly. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig12large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 13" class="xfigimg" src="/files/ftp_upload/56336/56336fig13.jpg" /> 
Figure 13: Presenting data. Examples of (a) a graphical data plot and (b) an intensity plot representing the spectrum of a 100 kA laboratory generated lightning arc in the 550 nm to 790 nm wavelength range. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig13large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 14" class="xfigimg" src="/files/ftp_upload/56336/56336fig14.jpg" /> 
Figure 14: Typical graphical data. A typical averaged, stitched, and corrected graphical plot in the 450 nm to 890 nm wavelength range for a 100 kA laboratory generated lightning arc. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig14large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 15" class="xfigimg" src="/files/ftp_upload/56336/56336fig15.jpg" /> 
Figure 15: Typical intensity plot. A typical averaged, stitched, and corrected intensity plot in the 450 nm to 890 nm wavelength range for a 100 kA laboratory generated lightning arc. <a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig15large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 16" class="xfigimg" src="/files/ftp_upload/56336/56336fig16.jpg" /> 
Figure 16: Chemical element identification. An illustration of spectral line chemical element identification for first order ionization levels using a publicly available database24. Elements in the air (nitrogen, oxygen, argon, helium) and in the electrode (tungsten) have been identified. This spectrum is near-identical to that in reference14 as it uses the same apparatus to analyze the same type of lightning arc. This figure has been adapted from reference14.&#160;<a href="https://cloudflare.jove.com/files/ftp_upload/56336/56336fig16large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

Watch this Scientific Journal Video about Method for Recording Broadband High Resolution Emission Spectra of Laboratory Lightning Arcs at JoVE.com

Method for Recording Broadband High Resolution Emission Spectra of Laboratory Lightning Arcs

Emission spectroscopy techniques have traditionally been used to analyze inherently random lightning arcs occurring in nature. In this paper, a method developed to obtain the emission spectroscopy from reproducible lightning arcs generated within a laboratory environment is described.

Lightning is one of the most common and destructive forces in nature and has long been studied using spectroscopic techniques, first with traditional ...

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6.9K Views.  Cardiff University. Emission spectroscopy techniques have traditionally been used to analyze inherently random lightning arcs occurring in nature. In this paper, a method developed to obtain the emission spectroscopy from reproducible lightning arcs generated within a laboratory environment is described.

Video: Method for Recording Broadband High Resolution Emission Spectra of Laboratory Lightning Arcs

Metal Flame Emission

<h4>Metal Flame Emission</h4>
Flame testing is an analytical technique where a sample is placed in a flame, and the characteristic flame color is used to identify the substance. Each element has a characteristic light emission when placed into a flame, meaning each element produces a unique color. This phenomenon is used in fireworks displays, where the color of the fireworks corresponds to a specific characteristic of a metal. The emission of colored light from a burning sample is the direct result of the metallic component absorbing energy due to the excitation from the flame and emitting light as a result.
<h4>Electron Excitement</h4>
When an atomic or molecular species absorbs energy, the energy is used in four different ways. First, the energy is used in translation, causing the molecules to move faster. Second, the energy is used in vibration, which causes the distance between the species to change rapidly. Third, the energy causes rotation, which induces the rotation of atoms around the bonds in the molecule. Finally, the absorbed energy results in electron excitement, which causes electrons to move to a higher energy level from the most stable or ground state.
According to the Bohr model of hydrogen, electrons in an atom exist in discrete states, which correspond to individual shells or orbitals around the nucleus. The lowest energy state is called the ground state and is represented by the notation of n = 1. Excited energy states have higher energies and are represented by the notation of n = 2, 3, 4, etc.
For electrons to move to a higher energy state, they must absorb an amount of energy that is equal to the difference between its ground state and the higher energy state. For example, if an electron absorbs an amount of energy that is equal to the difference between the ground state and the n=3 energy level, the electron will move to the n=3 energy level. An electron can spontaneously relax back down to the ground state or any other lower energy level. When this occurs, a photon is emitted, releasing the absorbed energy.
The released energy is emitted in the form of light. The emitted light has a characteristic energy, and therefore, wavelength, that correlates to the energy levels of the atom. Visible light, which is the light humans can see with their eyes, ranges from about 400 nm to 700 nm on the electromagnetic spectrum.
Atomic absorptions and emissions are discrete wavelengths, called lines. These lines are unique characteristics of an element, like a barcode, and can be used to identify the element.
<h4>Metal Flame Emission Test</h4>
In the metal flame emission test, a metal sample is placed in a flame. The flame provides the energy to excite electrons to a higher energy level. As the electrons relax back down to the ground state, light is emitted with a specific energy relative to the energy levels of the atoms in the sample. Since different atoms have different energy levels, the energy absorbed and emitted from a sample, and thus the wavelength, is specific to the sample.
Metals have characteristic atomic emission wavelengths in the visible range that are easily determined by visual inspection. For example, lithium emits a red color, sodium emits a yellow color, potassium emits a pink-purple color, and barium emits a yellow-green color.
While atomic emissions are discrete wavelengths or lines, most samples of metals contain not only the metal, but also various metal ions, oxides, and salts. Since each atom absorbs and emits a characteristic wavelength of light, the absorbed and emitted light from the flame test contains a range of wavelengths. Thus, atomic absorption and emission spectra can be measured for the sample using a spectrophotometer.
The wavelengths and shapes of the spectra are unique for each substance. For example, the relative intensity of features in the spectrum depends on the concentration of the species. The absolute intensities are dependent on the distance from the sample to the spectrophotometer.
<h4>References</h4>
<ol>
	<li style="font-size:17px">Kotz, J.C., Treichel Jr, P.M., Townsend, J.R. (2012). Chemistry and Chemical Reactivity. Belmont, CA: Brooks/Cole, Cengage Learning.</li>
	<li style="font-size:17px">Silderberg, M.S. (2009). Chemistry: The Molecular Nature of Matter and Change. Boston, MA: McGraw Hill.</li>
	<li style="font-size:17px">Harris, D.C. (2015). Quantitative Chemical Analysis. New York, NY: W.H. Freeman and Company.</li>
</ol>

Metal Flame Emission
Flame testing is an analytical technique where a sample is placed in a flame, and the characteristic flame color is used to identify ...

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Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet (VUV) Synchrotron Radiation

Tunable soft ionization coupled to mass spectroscopy is a powerful method to investigate isolated molecules, complexes and clusters and their spectroscopy and dynamics1-4. Fundamental studies of photoionization processes of biomolecules provide information about the electronic structure of these systems. Furthermore determinations of ionization energies and other properties of biomolecules in the gas phase are not trivial, and these experiments provide a platform to generate these data. We have developed a thermal vaporization technique coupled with supersonic molecular beams that provides a gentle way to transport these species into the gas phase. Judicious combination of source gas and temperature allows for formation of dimers and higher clusters of the DNA bases. The focus of this particular work is on the effects of non-covalent interactions, i.e., hydrogen bonding, stacking, and electrostatic interactions, on the ionization energies and proton transfer of individual biomolecules, their complexes and upon micro-hydration by water1, 5-9.
We have performed experimental and theoretical characterization of the photoionization dynamics of gas-phase uracil and 1,3-dimethyluracil dimers using molecular beams coupled with synchrotron radiation at the Chemical Dynamics Beamline10 located at the Advanced Light Source and the experimental details are visualized here. This allowed us to observe the proton transfer in 1,3-dimethyluracil dimers, a system with pi stacking geometry and with no hydrogen bonds1. Molecular beams provide a very convenient and efficient way to isolate the sample of interest from environmental perturbations which in return allows accurate comparison with electronic structure calculations11, 12. By tuning the photon energy from the synchrotron, a photoionization efficiency (PIE) curve can be plotted which informs us about the cationic electronic states. These values can then be compared to theoretical models and calculations and in turn, explain in detail the electronic structure and dynamics of the investigated species 1, 3.

Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation

A molecular beam coupled to tunable vacuum ultraviolet photoionization mass spectrometer at a synchrotron provides a convenient tool to explore the electronic structure of isolated gas phase molecules and clusters. Proton transfer mechanisms in DNA base dimers were elucidated with this technique.

Tunable soft ionization coupled to mass spectroscopy is a powerful method to investigate isolated molecules, complexes and clusters and their spectroscopy ...

Measurement and Analysis of Atomic Hydrogen and Diatomic Molecular AlO, C2, CN, and TiO Spectra Following Laser-induced Optical Breakdown

In this work, we present time-resolved measurements of atomic and diatomic spectra following laser-induced optical breakdown. A typical LIBS arrangement is used. Here we operate a Nd:YAG laser at a frequency of 10 Hz at the fundamental wavelength of 1,064 nm. The 14 nsec pulses with anenergy of 190 mJ/pulse are focused to a 50 &#181;m spot size to generate a plasma from optical breakdown or laser ablation in air. The microplasma is imaged onto the entrance slit of a 0.6 m spectrometer, and spectra are recorded using an 1,800 grooves/mm grating an intensified linear diode array and optical multichannel analyzer (OMA) or an ICCD. Of interest are Stark-broadened atomic lines of the hydrogen Balmer series to infer electron density. We also elaborate on temperature measurements from diatomic emission spectra of aluminum monoxide (AlO), carbon (C2), cyanogen (CN), and titanium monoxide (TiO).
The experimental procedures include wavelength and sensitivity calibrations. Analysis of the recorded molecular spectra is accomplished by the fitting of data with tabulated line strengths. Furthermore, Monte-Carlo type simulations are performed to estimate the error margins. Time-resolved measurements are essential for the transient plasma commonly encountered in LIBS.

Measurement and Analysis of Atomic Hydrogen and Diatomic Molecular AlO, C2, CN, and TiO Spectra Following Laser-induced Optical Breakdown

Time-resolved atomic and diatomic molecular species are measured using LIBS. The spectra are collected at various time delays following the generation of optical breakdown plasma with Nd:YAG laser radiation&#160;and are analyzed to infer electron density and temperature.

In this work, we present time-resolved measurements of atomic and diatomic spectra following laser-induced optical breakdown. A typical LIBS arrangement ...

Flame Experiments at the Advanced Light Source: New Insights into Soot Formation Processes

The following experimental protocols and the accompanying video are concerned with the flame experiments that are performed at the Chemical Dynamics Beamline of the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory1-4. This video demonstrates how the complex chemical structures of laboratory-based model flames are analyzed using flame-sampling mass spectrometry with tunable synchrotron-generated vacuum-ultraviolet (VUV) radiation. This experimental approach combines isomer-resolving capabilities with high sensitivity and a large dynamic range5,6. The first part of the video describes experiments involving burner-stabilized, reduced-pressure (20-80 mbar) laminar premixed flames. A small hydrocarbon fuel was used for the selected flame to demonstrate the general experimental approach. It is shown how species&#8217; profiles are acquired as a function of distance from the burner surface and how the tunability of the VUV photon energy is used advantageously to identify many combustion intermediates based on their ionization energies. For example, this technique has been used to study gas-phase aspects of the soot-formation processes, and the video shows how the resonance-stabilized radicals, such as C3H3, C3H5, and i-C4H5, are identified as important intermediates7. The work has been focused on soot formation processes, and, from the chemical point of view, this process is very intriguing because chemical structures containing millions of carbon atoms are assembled from a fuel molecule possessing only a few carbon atoms in just milliseconds. The second part of the video highlights a new experiment, in which an opposed-flow diffusion flame and synchrotron-based aerosol mass spectrometry are used to study the chemical composition of the combustion-generated soot particles4. The experimental results indicate that the widely accepted H-abstraction-C2H2-addition (HACA) mechanism is not the sole molecular growth process responsible for the formation of the observed large polycyclic aromatic hydrocarbons (PAHs).

Gas sampling from laboratory-scale flames with online analysis of all species by mass spectrometry is a powerful method to investigate the complex mixture of chemical compounds occurring during combustion processes. Coupled with tunable soft ionization via synchrotron-generated vacuum-ultraviolet radiation, this technique provides isomer-resolved information and potentially fragment-free mass spectra.

The following experimental protocols and the accompanying video are concerned with the flame experiments that are performed at the Chemical Dynamics ...

High Resolution Phonon-assisted Quasi-resonance Fluorescence Spectroscopy

High resolution optical spectroscopy methods are demanding in terms of either technology, equipment, complexity, time or a combination of these. Here we demonstrate an optical spectroscopy method that is capable of resolving spectral features beyond that of the spin fine structure and homogeneous linewidth of single quantum dots (QDs) using a standard, easy-to-use spectrometer setup. This method incorporates both laser and photoluminescence spectroscopy, combining the advantage of laser line-width limited resolution with multi-channel photoluminescence detection. Such a scheme allows for considerable improvement of resolution over that of a common single-stage spectrometer. The method uses phonons to assist in the measurement of the photoluminescence of a single quantum dot after resonant excitation of its ground state transition. The phonon&#39;s energy difference allows one to separate and filter out the laser light exciting the quantum dot. An advantageous feature of this method is its straight forward integration into standard spectroscopy setups, which are accessible to most researchers.

The manuscript describes a method of phonon-assisted quasi-resonant fluorescence spectroscopy that incorporates both laser-limited resolution and photoluminescence (PL) spectroscopy. This method utilizes optical phonons to provide linewidth-limited resolution spectra of atom-like semiconductor structures in the energy domain. The method is also easily realized with a single spectrometer optical spectroscopy setup.

High resolution optical spectroscopy methods are demanding in terms of either technology, equipment, complexity, time or a combination of these. Here we ...

Visualization of Ambient Mass Spectrometry with the Use of Schlieren Photography

This manuscript outlines how to visualize mass spectrometry ambient ionization sources using schlieren photography. In order to properly optimize the mass spectrometer, it is necessary to characterize and understand the physical principles of the source. Most commercial ambient ionization sources utilize jets of nitrogen, helium, or atmospheric air to facilitate the ionization of the analyte. As a consequence, schlieren photography can be used to visualize the gas streams by exploiting the differences in refractive index between the streams and ambient air for visualization in real time. The basic setup requires a camera, mirror, flashlight, and razor blade. When properly configured, a real time image of the source is observed by watching its reflection. This allows for insight into the mechanism of action in the source, and pathways to its optimization can be elucidated. Light is shed on an otherwise invisible situation.

This paper presents a protocol for the visualization of gaseous streams of an ambient ionization source using schlieren photography and mass spectrometry.

This manuscript outlines how to visualize mass spectrometry ambient ionization sources using schlieren photography. In order to properly optimize the mass ...

Emission Spectroscopic Boundary Layer Investigation during Ablative Material Testing in Plasmatron

Ablative Thermal Protection Systems (TPS) allowed the first humans to safely return to Earth from the moon and are still considered as the only solution for future high-speed reentry missions. But despite the advancements made since Apollo, heat flux prediction remains an imperfect science and engineers resort to safety factors to determine the TPS thickness. This goes at the expense of embarked payload, hampering, for example, sample return missions. 
Ground testing in plasma wind-tunnels is currently the only affordable possibility for both material qualification and validation of material response codes. The subsonic 1.2MW Inductively Coupled Plasmatron facility at the von Karman Institute for Fluid Dynamics is able to reproduce a wide range of reentry environments. This protocol describes a procedure for the study of the gas/surface interaction on ablative materials in high enthalpy flows and presents sample results of a non-pyrolyzing, ablating carbon fiber precursor. With this publication, the authors envisage the definition of a standard procedure, facilitating comparison with other laboratories and contributing to ongoing efforts to improve heat shield reliability and reduce design uncertainties.
The described core techniques are non-intrusive methods to track the material recession with a high-speed camera along with the chemistry in the reactive boundary layer, probed by emission spectroscopy. Although optical emission spectroscopy is limited to line-of-sight measurements and is further constrained to electronically excited atoms and molecules, its simplicity and broad applicability still make it the technique of choice for analysis of the reactive boundary layer. Recession of the ablating sample further requires that the distance of the measurement location with respect to the surface is known at all times during the experiment. Calibration of the optical system of the applied three spectrometers allowed quantitative comparison. At the fiber scale, results from a post-test microscopy analysis are presented.

Development of new ablative materials and their numerical modeling requires extensive experimental investigation. This protocol describes procedures for material response characterization in plasma flows with the core techniques being non-intrusive methods to track the material recession along with the chemistry in the reactive boundary layer by emission spectroscopy.

Ablative Thermal Protection Systems (TPS) allowed the first humans to safely return to Earth from the moon and are still considered as the only solution ...

Non-equilibrium Microwave Plasma for Efficient High Temperature Chemistry

A flowing microwave plasma based methodology for converting electric energy into internal and/or translational modes of stable molecules with the purpose of efficiently driving non-equilibrium chemistry is discussed. The advantage of a flowing plasma reactor is that continuous chemical processes can be driven with the flexibility of startup times in the seconds timescale. The plasma approach is generically suitable for conversion/activation of stable molecules such as CO2, N2 and CH4. Here the reduction of CO2 to CO is used as a model system: the complementary diagnostics illustrate how a baseline thermodynamic equilibrium conversion can be exceeded by the intrinsic non-equilibrium from high vibrational excitation. Laser (Rayleigh) scattering is used to measure the reactor temperature and Fourier Transform Infrared Spectroscopy (FTIR) to characterize in situ internal (vibrational) excitation as well as the effluent composition to monitor conversion and selectivity.

This article describes a flowing microwave reactor that is used to drive efficient non-equilibrium chemistry for the application of conversion/activation of stable molecules such as CO2, N2 and CH4. The goal of the procedure described here is to measure the in situ gas temperature and gas conversion.

A flowing microwave plasma based methodology for converting electric energy into internal and/or translational modes of stable molecules with the purpose ...

Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals

In this work, we describe a protocol for a novel application of hyperspectral imaging (HSI) in the analysis of luminescent lanthanide (Ln3+)-based molecular single crystals. As representative example, we chose a single crystal of the heterodinuclear Ln-based complex [TbEu(bpm)(tfaa)6] (bpm=2,2&#8217;-bipyrimidine, tfaa&#8211; =1,1,1-trifluoroacetylacetonate) exhibiting bright visible emission under UV excitation. HSI is an emerging technique that combines 2-dimensional spatial imaging of a luminescent structure with spectral information from each pixel of the obtained image. Specifically, HSI on single crystals of the [Tb-Eu] complex provided local spectral information unveiling variation of the luminescence intensity at different points along the studied crystals. These changes were attributed to the optical anisotropy present in the crystal, which results from the different molecular packing of Ln3+ ions in each one of the directions of the crystal structure. The HSI herein described is an example of the suitability of such technique for spectro-spatial investigations of molecular materials. Yet, importantly, this protocol can be easily extended for other types of luminescent materials (such as micron-sized molecular crystals, inorganic microparticles, nanoparticles in biological tissues, or labelled cells, among others), opening many possibilities for deeper investigation of structure-property relationships. Ultimately, such investigations will provide knowledge to be leveraged into the engineering of advanced materials for a wide range of applications from bioimaging to technological applications, such as waveguides or optoelectronic devices.

Here, we present a protocol to obtain luminescent hyperspectral imaging data and to analyze optical anisotropy features of lanthanide-based single crystals using a Hyperspectral Imaging System.

In this work, we describe a protocol for a novel application of hyperspectral imaging (HSI) in the analysis of luminescent lanthanide (Ln3+)-based ...

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis (FCLSA) on spectral data, in addition to CIE color coordinate determination and basic spectral processing. While some of the features may be found in commercial software or in programs made by&#160;academic research groups, we believe that ARL Spectral Fitting is the only application that possesses all three of the aforementioned attributes.
This program is intended as a standalone, GUI-based application for use by an average laboratory researcher without requiring any coding knowledge or proprietary software. In addition to the standalone executable hosted on ARL GitHub, the associated MATLAB files are available for use and further development.
FCLSA augments the information found in luminescence spectra, providing meaningful insight into the relationship between the ground and excited states of a photoluminescent species. This insight is achieved by modeling spectra with two versions (modes) of an equation that are characterized by either four or six parameters, depending on which mode is used. Once optimized, the value of each of these parameters can be used to gain insight into the molecule, as well as to perform further analysis (for example, the free energy content of the excited-state molecule). This application provides tools for easy by-hand fitting of imported data, as well as two methods for optimizing this fit-damped least-squares fitting, powered by the Levenberg-Marquardt algorithm, and derivative-free fitting utilizing the Nelder-Mead simplex algorithm. Furthermore, estimations of sample color can be performed and reported in CIE and RGB coordinates.

This protocol introduces Franck-Condon Lineshape Analyses (FCLSA) of emission spectra and serves as a tutorial for the use of ARL Spectral Fitting software. The open-source software provides an easy and intuitive way to perform advanced analysis of emission spectra including excited state energy calculations, CIE color coordinate determination, and FCLSA.

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis ...