absorption and emission of photons in organic compounds

Spectroscopy

Extremely high resolution spectrum of the Sun showing thousands of elemental absorption lines (fraunhofer lines) Spectroscopy is the study of matter and its properties by investigating light, sound, or particles that are emitted, absorbed or scattered by the matter under investigation. Spectroscopy may also be defined as the study of the interaction between light and matter. Historically, spectroscopy referred to a branch of science in which visible light was used

for theoretical studies on the structure of matter and for qualitative and quantitative analyses. ecently, however, the definition has broadened as new techniques have been developed that utili!e not only visible light, but many other forms of electromagnetic and non"electromagnetic radiation# microwaves, radiowaves, x"rays, electrons, phonons (sound waves) and others. Impedance spectroscopy is a study of frequency response in alternating current. Spectroscopy is often used in physical and analytical chemistry for the identification of substances through the spectrum emitted from them or absorbed in them. $ device for recording a spectrum is a spectrometer. Spectroscopy can be classified according to the physical quantity which is measured or calculated or the measurement process. Spectroscopy is also heavily used in astronomy and remote sensing. %ost large telescopes have spectrographs, which are used either to measure the chemical composition and physical properties of astronomical ob&ects or to measure their velocities from the 'oppler shift of spectral lines.

Contents ( )hysical quantity measured * %easurement process o *.( +hree main types of spectroscopy o *.* ,ommon types of spectroscopy *.*.( -lame Spectroscopy *.*.* .isible spectroscopy *.*./ 0ltraviolet spectroscopy *.*.1 2nfrared spectroscopy *.*.3 +hermal infrared spectroscopy *.*.4 5uclear magnetic resonance spectroscopy *.*.6 )hotoemission spectroscopy o *./ 7ess frequently used 8 combined spectroscopy o *.1 9uadratic ,ompression ,onversion (9,,) $lgorithm o *.3 :ac;ground Subtraction / See also

1 External lin;s

Physical quantity measured

+he type of spectroscopy depends on the physical quantity measured. 5ormally, the quantity that is measured is an amount or intensity of something.

+he intensity of emitted electromagnetic radiation and the amount of absorbed electromagnetic radiation are studied by electromagnetic spectroscopy (see also cross section). +he amplitude of macroscopic vibrations is studied by acoustic spectroscopy and dynamic mechanical spectroscopy. <inetic energy of particles is studied by electron energy loss spectroscopy and $uger electron spectroscopy (see also cross section). +he mass"to"charge ratios of molecules and atoms are studied in mass spectrometry, sometimes called mass spectroscopy. %ass spectrometry is more of a measuring technique (metric) than an observation (scopic) technique but can produce a spectrum of masses, a mass spectrum, similar in appearance to other spectroscopy techniques. +he number of molecules or atoms or quantum"mechanical states to which the frequency or energy parameter applies. 2n this case the

spectrum is usually called cross section.

Measurement process
'ifferent types of spectroscopy use different measurement processes#

Three main types of spectroscopy

Absorption spectroscopy uses the range of electromagnetic spectra in which a substance absorbs. 2n atomic absorption spectroscopy, the sample is atomi!ed and then light of a particular frequency is passed through the vapour. $fter calibration, the amount of absorption can be related to the concentrations of various metal ions through the :eer"7ambert law. +he method can be automated and is widely used to measure concentrations of ions such as sodium and calcium in blood. =ther types of spectroscopy may not require sample atomi!ation. -or example, ultraviolet8visible (0.8 .is) absorption spectroscopy is most often performed on liquid samples to detect molecular content and infrared (2 ) spectroscopy is most often performed on liquid, semi"liquid (paste,grease,and petroleum &elly), dried, or solid samples to determine molecular information, including structural information. Emission spectroscopy uses the range of electromagnetic spectra in which a substance radiates. +he substance first absorbs energy and then radiates this energy as light. +his energy can be from a variety of sources, including collision (either due to high temperatures or otherwise), and chemical reactions. Scattering spectroscopy measures certain physical properties by measuring the amount of light that a substance scatters at

certain wavelengths, incident angles, and polari!ation angles. Scattering spectroscopy differs from emission spectroscopy due to the fact that the scattering process is much faster than the absorption8emission process. =ne of the most useful applications of light scattering spectroscopy is aman spectroscopy.

Common types of spectroscopy

Spectrum of light from a fluorescent lamp showing prominent mercury pea;s. Fluorescence spectroscopy -luorescence spectroscopy uses higher energy photons to excite a sample, which will then emit lower energy photons. +his technique has become popular for its biochemical and medical applications, and can be used for confocal microscopy, fluorescence resonance energy transfer, and fluorescence lifetime imaging.

X ray spectroscopy and X ray crystallography >hen ?"rays of sufficient frequency (energy) interact with a substance, inner shell electrons in the atom are excited to outer empty orbitals, or they may be removed completely, ioni!ing the atom. +he inner shell @hole@ will then be filled by electrons from outer orbitals. +he energy available in this de"excitation process is emitted as radiation (fluorescence) or will remove other less"bound electrons from the atom ($uger effect). +he absorption or emission frequencies (energies) are characteristic of the specific atom. 2n addition, for a specific atom small frequency (energy) variations occur which are characteristic of the chemical bonding. >ith a suitable apparatus, these characteristic ?"ray frequencies or $uger electron energies can be measured. ?"ray absorption and emission spectroscopy is used in chemistry and material sciences to determine elemental composition and chemical bonding. ?"ray crystallography is a scattering processA crystalline materials scatter ?"rays at well"defined angles. 2f the wavelength of the incident ?"rays is ;nown, this allows calculation of the distances between planes of atoms within the crystal. +he intensities of the scattered ?"rays give information about the atomic positions and allow the arrangement of the atoms within the crystal structure to be calculated. Flame Spectroscopy 7iquid solution samples are aspirated into a burner or nebuli!er8burner combination, desolvated, atomi!ed, and sometimes excited to a higher energy electronic state. +he use of a flame during analysis requires fuel and oxidant, typically in the form of gases. ,ommon fuel gases used are acetylene (Ethyne) or hydrogen. ,ommon oxidant gases used are oxygen, air, or nitrous oxide. +hese methods are often capable of analy!ing metallic element analytes in the part per million, billion, or possibly lower concentration ranges. 7ight detectors are needed to detect light with the analysis information coming from the flame.

Atomic Emission Spectroscopy " +his method uses flame excitationA atoms are excited from the heat of the flame to emit light. +his method commonly uses a total consumption burner with a round burning outlet. $ higher temperature flame than atomic absorption spectroscopy ($$) is typically used to produce excitation of analyte atoms. Since analyte atoms are excited by the heat of the flame, no special elemental lamps to shine into the flame are needed. $ high resolution polychromator can be used to produce an emission intensity vs. wavelength spectrum over a range of wavelengths showing multiple element excitation lines, meaning multiple elements can be detected in one run. $lternatively, a monochromator can be set at one wavelength to concentrate on analysis of a single element at a certain emission line. )lasma emission spectroscopy is a more modern version of this method. See -lame emission spectroscopy for more details. Atomic absorption spectroscopy (often called $$) " +his method commonly uses a pre"burner nebuli!er (or nebuli!ing chamber) to create a sample mist and a slot" shaped burner which gives a longer pathlength flame. +he temperature of the flame is low enough that the

flame itself does not excite sample atoms from their ground state. +he nebuli!er and flame are used to desolvate and atomi!e the sample, but the excitation of the analyte atoms is done by the use of lamps shining through the flame at various wavelengths for each type of analyte. 2n $$, the amount of light absorbed after going through the flame determines the amount of analyte in the sample. $ graphite furnace for heating the sample to desolvate and atomi!e is commonly used for greater sensitivity. +he graphite furnace method can also analy!e some solid or slurry samples. :ecause of its good sensitivity and selectivity, it is still a commonly used method of analysis for certain trace elements in aqueous (and other liquid) samples. Atomic Fluorescence Spectroscopy " +his method commonly uses a burner with a round burning outlet. +he flame is used to solvate and atomi!e the sample, but a lamp shines light at a specific wavelength into the flame to excite the analyte atoms in the flame. +he atoms of certain elements can then fluoresce emitting light in a different direction. +he intensity of this fluorescing light is used for quantifying the amount of analyte

element in the sample. $ graphite furnace can also be used for atomic fluorescence spectroscopy. +his method is not as commonly used as atomic absorption or plasma emission spectroscopy. Plasma Emission Spectroscopy 2n some ways similar to flame atomic emission spectroscopy, it has largely replaced it.

'irect"current plasma (',)) Blow discharge"optical emission spectrometry (B'"=ES) 2nductively coupled plasma"atomic emission spectrometry (2,)"$ES) 7aser 2nduced :rea;down Spectroscopy (72:S) (72:S), also called 7aser"induced plasma spectrometry (72)S) %icrowave"induced plasma (%2))

Spar! or arc "emission# spectroscopy " is used for the analysis of metallic elements in solid samples. -or non"conductive materials, a sample is ground with graphite powder to ma;e it conductive. 2n traditional arc spectroscopy methods, a sample of the solid was commonly ground up and destroyed during analysis. $n electric arc or spar; is passed through the sample, heating the sample to a high temperature to excite the atoms in it. +he excited analyte atoms glow emitting light at various wavelengths which could be detected by common spectroscopic methods. Since the conditions producing the arc emission typically are not controlled quantitatively, the analysis for the elements is qualitative. 5owadays, the spar; sources with controlled discharges under an argon atmosphere allow that this method can be considered eminently quantitative, and its use is

widely expanded worldwide through production control laboratories of foundries and steel mills.

$isible spectroscopy %any atoms emit or absorb visible light. 2n order to obtain a fine line spectrum, the atoms must be in a gas phase. +his means that the substance has to be vaporised. +he spectrum is studied in absorption or emission. .isible absorption spectoscopy is often combined with 0. absorption spectroscopy in 0.8.is spectroscopy.

%ltra&iolet spectroscopy $ll atoms absorb in the 0. region because photons are energetic enough to excite outer electrons. 2f the frequency is high enough, photoionisation ta;es place.

Infrared spectroscopy Main article: Infrared spectroscopy 2nfrared spectroscopy offers the possibility to measure different types of interatomic bond vibrations at different frequencies. Especially in organic chemistry the analysis of 2 absorption spectra shows what type of bonds are present in the sample.

Thermal infrared spectroscopy

Main article: Thermal infrared spectroscopy +hermal infrared spectroscopy measures thermal radiation emitted from materials and surfaces and is used to determine the type of bonds present in a sample as well as their lattice environment. +he techniques are widely used by organic chemists, mineralogists, and planetary scientists. +his type of spectroscopy is great for small children and animals of miniscule si!es.

'uclear magnetic resonance spectroscopy Main article: NMR spectroscopy 5uclear magnetic resonance spectroscopy analy!es certain atomic nuclei to determine different local environments of hydrogen, carbon, or other atoms in the molecule of an organic compound or other compound. +his is used to help determine the structure of the compound.

Photoemission spectroscopy

(ess frequently used ) combined spectroscopy

aman spectroscopy uses the inelastic scattering of light to analyse vibrational and rotational modes of molecules. +he resulting CfingerprintsC are an aid to analysis. 2nelastic neutron scattering wor;s li;e aman spectroscopy, with neutrons instead of light.

aman =ptical $ctivity spectroscopy exploits aman scattering and optical activity effects to reveal detailed information on chiral centres in molecules. $uger electron spectroscopy is a method used to study surfaces of materials on a micro"scale. 2t is often used in connection with electron microscopy. -ourier transform is an efficient method for collecting various spectra. +he use of -ourier transform in spectroscopy is called -ourier transform spectroscopy. 5early all infrared spectroscopy (-+2 ) and nuclear magnetic resonance (5% ) spectroscopy are performed with -ourier transforms. Spectroscopy of matter in situations where the properties are changing with time is called +ime"resolved spectroscopy. Spectroscopy using an $-%"based analytical technique is called -orce spectroscopy. 'ielectric spectroscopy ,ircular 'ichroism spectroscopy ,avity ring down spectroscopy

*uadratic Compression Con&ersion "*CC# Algorithm

+he 9,, algorithm is a transform used in spectroscopic applications. +ransforms have been used for many years to enhance statistics D for example the --+ algorithm used to enhance x"ray imaging. 9,, is based on an algorithm related to the square root of the isotopeEs energy line(s). +his optimi!es the spectrum so that pea;s are well separated at high, low, and all energies in between. 2n conventional spectroscopy you can optimi!e the low energy at the expense of the high energy and vice versa. $ll pea;s in the 9,, spectrum fall into eleven channels. 9,, allows isotopes with low branching intensities to be identified in real time. +he sensitivity arising from one"second data slices is greatly improved even down to bac;ground levels. -or example, (/6,s at (F microrem8h yields a sigma (standard deviation) above bac;ground of almost *F#( in one second. +his is important when identifying uranium and weapons"grade plutonium since these are best identified by their low abundant lines. 9,, provides improvements in compensating for the drift of radiation detectors. Since the compression is a function of energy, the drift will be nearly compensated over a range of G8" (H I-. 9,, technology is of particular importance in applications where a wide energy range must be monitored for un;nown sources of radiation. +he 9,, process ma;es detection of pea;s at all energies equally straight forward. )ea;s at low energies are well resolved, while at high energies pea;s are compressed so that the pea; to bac;ground ratio is dramatically improved for a given number of counts. +his directly translates into shorter counting times with better identification and analysis. -or more on 9,,, see J9,, advantagesK at www.ber;eleynucleonics.com, 9,, )atent 'etails at www.pgt.com , 7arge Scale 'emonstration and 'eployment )rogram at www.ineel.gov

+ac!ground Subtraction
:ac;ground subtraction is a term typically used in spectroscopy when one explains the process of acquiring a bac;ground radiation level (or ambient radiation level) and then ma;es an algorithmic ad&ustment to the data to obtain qualitative information about any deviations from the bac;ground, even when they are an order of magnitude less decipherable than the bac;ground itself. :ac;ground subtraction can effect a number of statistical calculations (,ontinuum, ,ompton, :remsstrahlung) leading to improved overall system performance.