Car–Parrinello method: Difference between revisions

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There is nothing "ab initio" about the method; you have free parameters (the fictitious mass of the electron). Ab initio requires no free parameters.
 
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{{Infobox chemical analysis
Name: Latasha Mcintire<br>My age: 28 years old<br>Country: Netherlands<br>Town: Maastricht <br>ZIP: 6217 Ke<br>Street: Statensingel 99<br><br>My web page - Fifa 15 Coin Generator ([http://Moodygoods.com/system-cgi/blog/index.php?itemid=1824&catid=499 Moodygoods.com])
| name = Fourier transform ion cyclotron resonance
| image =
| caption =A FTMS instrument at the [[Pacific Northwest National Laboratory]], USA
| acronym = FTICR
| classification =[[Mass spectrometry]]
| analytes =
| manufacturers =
| related = [[Ion trap]]<br>[[Quadrupole ion trap]]<br>[[Penning trap]]<br>[[Orbitrap]]
| hyphenated =
}}
'''Fourier transform ion cyclotron resonance mass spectrometry''' is a type of mass analyzer (or [[mass spectrometer]]) for determining the [[mass-to-charge ratio]] ''(m/z'') of [[ions]] based on the [[ion cyclotron resonance|cyclotron frequency]] of the ions in a fixed magnetic field.<ref name="primer">[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=9768511 Marshall, A. G.; Hendrickson, C. L.; Jackson, G. S., Fourier transform ion cyclotron resonance mass spectrometry: a primer. ''Mass Spectrom Rev'' '''17''', 1-35.]</ref> The ions are trapped in a [[Penning trap]] (a magnetic field with electric trapping plates) where they are excited (at their resonant cyclotron frequencies) to a larger cyclotron radius by an oscillating electric field orthogonal to the magnetic field. After the excitation field is removed, the ions are rotating at their cyclotron frequency in phase (as a "packet" of ions). These ions induce a charge (detected as an image current) on a pair of electrodes as the packets of ions pass close to them. The resulting signal is called a [[free induction decay]] (FID), transient or interferogram that consists of a superposition of [[sine waves]]. The useful signal is extracted from this data by performing a [[Fourier transform]] to give a [[mass spectrum]]. There are many mass spectrometry ionization techniques that undergo a [[Fourier transform]], therefore it is incorrect to refer to this technique as Fourier transform mass spectrometry. <ref>{{cite book |last=Skoog |first=Douglas |year=2007 |title=Principles of Instrumental Analysis (6th Ed)}}</ref>
 
Fourier transform ion cyclotron resonance (FTICR) mass spectrometry is a very high resolution technique that can be used to determine masses with very high accuracy. Many applications of FTICR-MS use this mass accuracy to help determine the composition of molecules based on accurate mass. This is possible due to the [[mass defect]] of the elements. FTICR-MS is able to achieve higher levels of resolution than other forms of [[mass spectrometers|mass spectrometer]], in part, because a superconducting magnet is much more stable than RF ([[radio frequency]]) voltage.<ref>{{Cite journal | doi = 10.1016/S1387-3806(99)00226-2 | title = Comparison and interconversion of the two most common frequency-to-mass calibration functions for Fourier transform ion cyclotron resonance mass spectrometry | first5 = Alan G. | last5 = Marshall | first4 = Christopher L. | last4 = Hendrickson | first3 = Michael A. | last3 = Freitas | first2 = Jared J. | year = 2000 | last2 = Drader | last1 = Shi | first1 = S | journal = International Journal of Mass Spectrometry | volume = 195-196 | pages = 591 }}</ref>  Another place that FTICR-MS is useful is in dealing with complex mixtures since the resolution (narrow peak width) allows the signals of two ions of similar mass to charge (''m/z'') to be detected as distinct ions.<ref name="pmid15694769">{{Cite journal |author=Sleno L, Volmer DA, Marshall AG |title=Assigning product ions from complex MS/MS spectra: the importance of mass uncertainty and resolving power |journal=[[J. Am. Soc. Mass Spectrom.]] |volume=16 |issue=2 |pages=183–98 |date=February 2005 |pmid=15694769 |doi=10.1016/j.jasms.2004.10.001 |url=}}</ref><ref name="pmid12033259">{{cite journal |author=Bossio RE, Marshall AG |title=Baseline resolution of isobaric phosphorylated and sulfated peptides and nucleotides by electrospray ionization FTICR ms: another step toward mass spectrometry-based proteomics |journal=[[Anal. Chem.]] |volume=74 |issue=7 |pages=1674–9 |date=April 2002 |pmid=12033259 |doi= 10.1021/ac0108461|url=}}</ref><ref name="pmid11217775">{{cite journal |author=He F, Hendrickson CL, Marshall AG |title=Baseline mass resolution of peptide isobars: a record for molecular mass resolution |journal=[[Anal. Chem.]] |volume=73 |issue=3 |pages=647–50 |date=February 2001 |pmid=11217775 |doi= 10.1021/ac000973h|url=}}</ref> This high resolution is also useful in studying large macromolecules such as proteins with multiple charges which can be produced by [[electrospray ionization]]. For example, attomole level of detection of two peptides has been reported .<ref name="pmid8633766">{{cite journal |author=Solouki T, Marto JA, White FM, Guan S, Marshall AG |title=Attomole biomolecule mass analysis by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance |journal=[[Anal. Chem.]] |volume=67 |issue=22 |pages=4139–44 |date=November 1995 |pmid=8633766 |doi= 10.1021/ac00118a017|url=}}</ref>  These large molecules contain a distribution of [[isotopes]] that produce a series of isotopic peaks. Because the isotopic peaks are close to each other on the ''m/z'' axis, due to the multiple charges, the high resolving power of the FTICR is extremely useful.
 
FTICR-MS differs significantly from other [[mass spectrometry]] techniques in that the ions are not detected by hitting a detector such as an [[electron multiplier]] but only by passing near detection plates. Additionally the masses are not resolved in space or time as with other techniques but only by the cyclotron (rotational) frequency that each ion produces as it rotates in a magnetic field. Thus, the different ions are not detected in different places as with [[sector instrument]]s or at different times as with [[time-of-flight]] instruments but all ions are detected simultaneously during the detection interval. This provides an increase in the observed [[signal to noise ratio]] owing to the principles of [[Fellgett's advantage]].<ref name="primer"/> In FTICR-MS, resolution can be improved either by increasing the strength of the magnet (in [[Tesla (unit)|teslas]]) or by increasing the detection duration.<ref>{{Cite journal | doi = 10.1016/S1387-3806(01)00588-7 | title = Fourier transform ion cyclotron resonance detection: principles and experimental configurations | year = 2002 | last1 = Marshall | first1 = A | journal = International Journal of Mass Spectrometry | volume = 215 | pages = 59 }}</ref>
 
==History==
FT-ICR was invented by Melvin B. Comisarow and [[Alan G. Marshall]]<ref>{{cite web|url=http://www.chem.ubc.ca/personnel/faculty/comisarow/ |title=UBC Chemistry Personnel: Melvin B. Comisarow |accessdate=2009-11-05 |publisher=University of British Columbia }}</ref> at the [[University of British Columbia]]. The first paper appeared in [[Chemical Physics Letters]] in 1974.<ref>[http://dx.doi.org/10.1016/0009-2614(74)89137-2 M.B. Comisarow and A.G. Marshall, ''Chem. Phys. Lett.'' '''25''', 282 (1974)]</ref> The inspiration was earlier developments in conventional ICR and Fourier Transform Nuclear Magnetic Resonance (FT-NMR) spectroscopy. Marshall has continued to develop the technique at [[Ohio State University|The Ohio State University]] and [[Florida State University]].
 
==Theory==
[[Image:LTQ-FTICR.jpg|thumb|250px|Linear ion trap - Fourier transform ion cyclotron resonance mass spectrometer (panels around magnet are missing).]]
The physics of FTICR is similar to that of a [[cyclotron]] at least in the first approximation.
 
In the simplest form (idealized) the relationship between the cyclotron frequency and the mass to charge ratio is given by:
 
:<math>f = \frac{qB}{2\pi m}</math>
 
where ''f'' = cyclotron frequency, ''q'' = ion charge, ''B'' = [[magnetic field strength]] and ''m'' = ion mass.
 
This is more often represented in [[angular frequency]]:
 
:<math>\omega _c = \frac{qB}{m}</math>
 
where <math>\omega _c</math> is the angular cyclotron frequency which is related to frequency by the definition <math>f = \frac{\omega}{2\pi}</math>.
 
Because of the quadrupolar electrical field used to trap the ions in the axial direction this relationship is only approximate. The axial electrical trapping results in axial oscillations within the trap with the (angular) frequency:
 
:<math>\omega _t = \sqrt{{\frac{q\alpha}{m}}}</math>
 
Where <math>\alpha</math> is a constant similar to the spring constant of a [[harmonic oscillator]] and is dependent on applied voltage, trap dimensions and trap geometry.
 
The electric field and the resulting axial harmonic motion reduces the cyclotron frequency and introduces a second radial motion called magnetron motion that occurs at the magnetron frequency. The cyclotron motion is still the frequency being used but the relationship above is not exact due to this phenomenon. The natural angular frequencies of motion are:
 
:<math>\omega _\pm = \frac{\omega _c}{2} \pm \sqrt{\left({\frac{\omega _c}{2}}\right)^2-{\frac{\omega _t^2}{2}}}</math>
 
where <math>\omega _t</math> is the axial trapping frequency due the axial electrical trapping and <math>\omega _+</math> is the reduced cyclotron (angular) frequency and <math>\omega _-</math> is the magnetron (angular) frequency. Again <math>\omega _+</math> is what is typically measured in FTICR. The meaning of this equation can be understood qualitatively by considering the case where  <math>\omega _t</math> is small, which is generally true. In that case the value of the radical is just slightly less than <math>\omega_c/2</math> and the value of <math>\omega _+</math> is just slightly less than <math>\omega_c</math> (the cyclotron frequency has been slightly reduced). For <math>\omega_-</math> the value of the radical is the same (slightly less than <math>\omega_c/2</math>) but it is being subtracted from <math>\omega _c/2</math> resulting in a small number equal to <math>\omega _c -\omega _+</math> (i.e. the exact amount that the cyclotron frequency was reduced by).
 
==ICR cell types==
[[Image:ICR Cell.jpg|thumb|250px|A cylindrical ICR cell. The walls of the cell are made of copper, and ions enter the cell from the right, transmitted by the octopole ion guides.]]
A review of different cell geometries with their specific electric configurations is available in the literature.<ref>[http://dx.doi.org/10.1016/0168-1176(95)04190-V S. Guan, A. G. Marshall, Int. J. Mass Spectrom., 146/147 (1995) 261]</ref>  However, ICR cells can belong to one of the following two categories.
 
===Closed cells===
 
Several closed ICR cells with different geometries were fabricated and their performance has been characterized. Grids were used as end caps to apply an axial electric field for trapping ions axially (parallel to the magnetic field lines). Ions can be either generated inside the cell or can be injected to the cell from an external [[ion source|ionization source]]. Nested ICR cells with double pair of grids were also fabricated to trap both positive and negative ions simultaneously.
 
===Open cells===
The most common geometry is a cylinder, which is axially segmented to produce electrodes in the shape of a ring. The central ring electrode is commonly used for applying radial excitation electric field and detection. DC electric voltage is applied on the terminal ring electrodes to trap ions along the magnetic field lines.{{citation needed|date=November 2012}} Open cylindrical cells with ring electrodes of different diameters have also been designed.<ref>{{Cite journal | doi = 10.1063/1.2751100 | title = Characterization of a new open cylindrical ion cyclotron resonance cell with unusual geometry | year = 2007 | last1 = Kanawati | first1 = B. | first2 = K. P. | journal = Review of Scientific Instruments | volume = 78 | pages = 074102 | pmid = 17672776 | last2 = Wanczek | issue = 7 |bibcode = 2007RScI...78g4102K }}</ref> They proved not only capable in trapping and detecting both ion polarities simultaneously, but also they succeeded to separate positive from negative ions radially. This presented a large discrimination in kinetic ion acceleration between positive and negative ions trapped simultaneously inside the new cell. Several ion axial acceleration schemes were recently written for ion-ion collision studies <ref>{{Cite journal | doi = 10.1016/j.ijms.2007.09.007 | title = Characterization of a new open cylindrical ICR cell for ion–ion collision studies☆ | year = 2008 | last1 = Kanawati | first1 = B | first2 = K | journal = International Journal of Mass Spectrometry | volume = 269 | pages = 12 | last2 = Wanczek|bibcode = 2008IJMSp.269...12K }}</ref>
 
==Stored waveform inverse Fourier transform ==
Stored waveform inverse Fourier transform (SWIFT) is a method for the creation of excitation waveforms for FTMS.<ref name=Cody1987>{{Cite journal | last = Cody | first =  R. B. | year = 1987 | title = Stored waveform inverse fourier transform excitation for obtaining increased parent ion selectivity in collisionally activated dissociation: Preliminary results | journal = [[Rapid Communications in Mass Spectrometry]] | volume = 1 | pages = 99 | doi = 10.1002/rcm.1290010607 | first2 = R. E. | first3 = S. D. | first4 = Alan G. | last2 = Hein | last3 = Goodman | last4 = Marshall | issue = 6}}</ref> The time-domain excitation waveform is formed from the inverse Fourier transform of the appropriate frequency-domain excitation spectrum, which is chosen to excite the resonance frequencies of selected ions. The SWIFT procedure can be used to select ions for [[tandem mass spectrometry]] experiments.
 
==See also==
*[[Ion cyclotron resonance]]
 
==External links==
* [http://www.magnet.fsu.edu/science/cimar/icr/ National High Field Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry facility, Tallahassee, Florida, USA]
* [http://www.magnet.fsu.edu/education/tutorials/magnetacademy/fticr/ What's in an Oil Drop? An Introduction to Fourier Transform Ion Cyclotron Resonance (FT-ICR) for Non-scientists] National High Magnetic Field Laboratory
*[http://www.sircams.ed.ac.uk Scottish Instrumentation Resource Centre for Advanced Mass Spectrometry]
*[http://www.chm.bris.ac.uk/ms/theory/fticr-massspec.html Fourier-transform Ion Cyclotron Resonance (FT-ICR)] FT-ICR Introduction University of Bristol
 
==References==
{{Reflist|2}}
 
{{Mass spectrometry}}
 
{{DEFAULTSORT:Fourier Transform Ion Cyclotron Resonance}}
[[Category:Mass spectrometry]]
[[Category:Measuring instruments]]

Latest revision as of 02:31, 24 March 2014

Name: Latasha Mcintire
My age: 28 years old
Country: Netherlands
Town: Maastricht
ZIP: 6217 Ke
Street: Statensingel 99

My web page - Fifa 15 Coin Generator (Moodygoods.com)