Académique Documents
Professionnel Documents
Culture Documents
ar on
Tino Woodburn March 2013 Abstract for Laser Applications by Dr. Rufus Cone R M!" #Resonance nhanced Multi !hoton "oni$ation% is a techni&ue that uses laser li'ht to e(cite s)all )olecules or ato)s to inter)ediate states and ioni$e the) *ithin the sa)e pulse of li'ht. The resonant electronically e(cited inter)ediate states are sti)ulated as &uic+ly as picosecond. Thus a fe* nanosecond laser pulse *ith hi'h enou'h intensity is sufficient to ioni$e the )olecule, this can be a )ore than a t*o photon absorption techni&ue. R M!" can 'i-e spectroscopic infor)ation such as rotational states and hi'h Rydber' state that are not achie-able *ith sin'le photon )ethods. Dependin' on *hat the ener'y le-els are bein' probed certain *a-elen'ths )ust be used. The laser in use is a .D /000 Continuu) Dye Laser usin' DCM dye doubled to 310 *hich e(cite the C1 #carbon )ono(ide% )olecule. 2ecause the laser is not in a(is *ith the interaction re'ion !ellin32roca pris)s and )irrors to ali'n the laser throu'h a *indo* into a -acuu) cha)ber. The dye laser is pu)ped by a !o*erlite .d3456A7 *hich also uses a nonlinear optical crystal to use the second har)onic of 832n). The hyperther)al o(y'en is obtained by detonation of 12 *ith a C12 laser *ith 0 *att9pulse. A $inc selenite *indo* and a 'old )irror are used in con:unction *ith a -acuu) cha)ber to create a pulsed bea) of 'round state ato)ic o(y'en #1 triplet p%. The carbon is ablated by a ;urelite .d3456A7 laser tripled to 38< n) or an e(ci)er laser usin' +rypton fluoride *hich lasin' at 2<=n), the *a-elen'th difference can cause differences in the ablated carbon *hich is carried by a pulsed inert 'as. This )ust all be ali'ned in ti)e and space to collide in a re'ion *hich is pic+ed up by ion optics and accelerated to a scintillator up ne(t to a hi'h )e'api(el CCD #char'e3coupled de-ice%. This paper *ill 'i-e a thorou'h o-er-ie* of the technolo'y and )aterials used to construct this apparatus.
Introduction:
What is ;pectroscopy> The study of )olecular structure and dyna)ics throu'h the absorption, )ission, and scatterin' of li'ht
http599***.pci.tu3bs.de9a''eric+e9!C<e9inde(.ht)l Crossed )olecular bea) scatterin' has co)pletely chan'ed our understandin' the dyna)ics of che)ical reactions *hich is a reason 6uan T. Lee and ?ohn C. !olanyi and Dudley R. @erschbach *on the .obel !ri$e in 1A=/ Bfor their contributions of to the dyna)ics of che)ical ele)entary processes.C 6.T. LeeDs *or+ in the use of crossed )olecular bea)s pioneered the *ay ener'y )easure)ents of )olecules and ato)s are ac&uired. The dyna)ics of ele)entary che)ical reactions can be calculated +no*in' an'ular and -elocity distributions. E6uan T. Lee 3 .obel Lecture5 Molecular 2ea) ;tudies of le)entary Che)ical !rocessesE. .obelpri$e.or'. 22 Apr 2013 http599***.nobelpri$e.or'9nobelFpri$es9che)istry9laureates91A=/9lee3lecture.ht)l This lead Chandler and @ouston to loo+ deeper into the rotational and -ibrational ener'ies of reactions by probin' the reactant *ith polari$ed laser li'ht. BThe recoil an'le, *ith respect to the polari$ation -ector of the dissociatin' li'ht, 'i-es additional infor)ation about the transition )o)ent in the parent )olecule and the ti)e scale of dissociation.C A t*o di)ensional surface such as a CCD can )easure a three di)ensional distribution of the photofra')ents and Doppler techni&ues are then used to calculate -ibrational and rotational ener'ies of the
products. This procedure beca)e +no*n as Resoncance nhanced Multi !hoton "oni$ation #R M!"% ?. Che). !hys. =0, 1<<8 #1A=0%G doi5 10.10/391.<8320/
".
R M!" 3 3 Detailed e(planation of 241 )ulti photon absorption in the sin'le pulse.
"". a. Lasers, both dye and pu)pin' lasers i. Choosin' correct *a-elen'th to e(cite and then ioni$e the reactants b. Wa-elen'th Ran'e Wa-eMasterHto ensure the correct ener'y *hich uses fiber optics i. 3=0 n) to 10A8 n) ii. 0.008 n) accuracy iii. 0.001 nm resolution Max. Signal Bandwidth 2 nm @ 400 nm3 nm @ 600 nm5 nm @ 1000
nm
i-. The Wa-eMaster is a hi'h diffraction order spectro)eter. Wa-ele'hth is deter)ined by careful )easure)ent of the separation bet*een the diffracted orders. Much of the accuracy and si)plicity in use is achie-ed throu'h soft*are i)ple)ented al'orith)s runnin' in the di'ital si'nal processor and con-entional )icroprocessor in the instru)ent.
-. The Wa-eMaster )easures the *a-elen'th of both CW and pulsed lasers of any repetition rate. The *a-elen'th can be displayed in 7@$, *a-enu)bers, or nano)eters *ith -acuu) and air readin's a-ailable.
-i. c. Ali'n)ent i. Location, Location, Location d. Ti)in' and delays i. Ti)in' is essential to all the sinners and saints but *hen tryin' to deter)ine the )echanics and ener'y of ato)s collidin' *ith each other it is on a co)pletely different le-el. This ti)in' ta+es ti)e and a 'ood understandin' of all the processes 'oin' on in the syste). Iirst *e *ill i)a'ine the apparatus. The 800 psi pulse of )olecular o(y'en )ust be released around 1A3Js before the C12 laser is fired #if the laser is fired too early there *ill not be enou'h o(y'en to absorb the ener'y of the laser pulse and the copper cone *ill be catastrophically da)a'ed%. The C12 laser has a pulse len'th of K2.8 Js dependin' on the )i(ture of 'as. "f the laser is fired )icro second too late the pulse of o(y'en *ill be ahead of the focused laser bea) )eanin' a portion of the o(y'en )olecules *ill not be bro+en into ato)ic o(y'en 'i-in' lo*er yields of the C1 product. The laser ablation of the carbon rod needs to happen )icroseconds before the pulse of carrier 'as #ar'on% en'ulfs the ablated carbon carryin' the carbon into the reaction re'ion. 2oth of these pulses of 'as the ato)ic o(y'en #a plas)a *hich is tra-elin' )uch faster than
the ori'inal pulse of o(y'en, ther)al -s. hyperther)al% and the ablated carbon bein' carried by ar'on )ust )eet in the reaction re'ion directly belo* the ion optics in the sa)e ti)e and space as the fre&uency selected laser that *ill e(cite the C1 )olecule to a )etastable state +no*n as a Rydber' state and then co)pletely strip the )olecule of the e(cited electron all in the sa)e -ery short pulse of li'ht. This ion, C14 is then accelerated to to*ard the detector by the ion optics. The detector )ust be s*itch on and then off at the correct ti)e to 'i-e a ti)e sliced -elocity i)a'e. The delay is chosen to be lon' enou'h to allo* suficient product density to build up prior to the detection step, but also suLciently short to ensure that the product distribution is nascent at the instant of detection and that no post3reacti-e collisions ha-e occurred #i.e., under sin'le collision conditions%. The delay )ust also be short enou'h to ensure that prod3ucts for)ed *ith the hi'hest -elocities do not escape the probe laser interaction re'ion before they can be ionised #i.e., fly3out is a-oided%.Dr.2ass !hD.Thesis ora.ox.ac.uk/objects/uuid:ea381f05-6a68-435f-
91d6.../THES S0!
ii. iii. Ti)in' is essential as *e ha-e *ell learned if you *ant to 'uess at the ti)in' of ato)s and electrons you need to consult @eisenber', MTM N 1033< ? s. Meanin' if you are 'oin' to 'uess you need to be *ithin 1033< seconds. Therefore *e *ill not 'uess. Calculatin' the e. "on 1ptics
f.
Detector i. MC!, CCD, !hosphorous, di'ital readout of the -ibration and rotation le-els.
a. b. Laser in use and other lasers that can be used coolin' syste)s, c. .d56A, e(ci)er d. Molecular bea)s of s)all carbon clusters *ill be 'enerated usin' a laser
ablation source based on the desi'n by Qaiser and co3*or+ers. 0 #0% 7u, R.G 7uo, 6.G Qa*a)ura, .G Qaiser, R. ". "# $ac# %ci# &echnol# A# 2006, '(, 808
e. products of ablation *ith respect to the po*er and type of )aterial used. f. an'les of incidence,
+. Laser Doppler Oeloci)etry of the source of o(y'en. l. !article ")a'in' Oeloci)etry o f the source and the reaction.
). Molecular 2ea) pita(y *ith laser detonated 'ases to produce better optical )aterial O"". Ato)ic 1(y'en a. C12 Laser le-els and sche)atics. Tse the patent C;ource of hi'h flu( ener'etic ato)sC i. http599***.laser+.co)9ne*sletters9inde(.ht)l ii. ;hape of bea), intensity, repetition, iii. 7as analysis, pea+ po*er of bea) b. Copper cone c. !ie$eioelectric pulse -al-e and pressure d. A)ount of photons and )olecules collidin' about 3.8e20 photons
e. ;peed and ener'y transfer of the photons *ith the )olecules and the brea+do*n of the )olecule into ato)ic o(y'en f. Reacti-ity and use for this type of ato)ic o(y'en bea)
'. Cleanin' and )aintenance of the laser O""". ali'n)entS Theory of Laser ali'n)ent of the source. a.
!" LAS#$
http599***.iap.tu3dar)stadt.de9lpp9co2s9co2.ht)l Institut fr Angewandte Physik Technische Universitt Darmstadt Schl gartenstrasse ! D 6"2#$ Darmstadt %ermany
2R11Q; 33 lectronically or hi'hly -ibrationally e(cited C1 has lon' been +no*n as )olecule capable of bein' used in a che)ical laser.133 #1% !ollac+, M. A. Appl. !hys. Lett. 1A//, =, 230.
#2% 2arano-, ". 6. Uuantu) lectronics 1AA<, 2<, 83/. #3% !atel, C. Q. ..G Qerl, R. ?. Appl. !hys. Lett. 1A/<, 8, =1. T&A laser is a trans-ersely3e(cited at)ospheric3pressure laser. C Q . !atel, *or+in' at the 2ell Telephone Laboratories in 1A/3, first de)onstrated laser output at 10./ J) fro) a lo* pressure RI e(cited C12 'as dischar'e.#3% Alltec #a Oideo:et co)pany% sells a C12 T A laser called the All)ar+ A!; *hich is sold as a )ar+in' laser for products. They boast the Bs)allest si$e and *ei'ht, lo*est operation, spare parts and ser-ice costs.C "t is about one )eter lon', half a )eter *ide and hi'h stainless steel housin' *ei'hin' 122+', *ith a separate coolin' syste) usin' 132 l9)in at 10328 VC. The *a-elen'ths of A.3 J) or 10./ J) can be selectable by si)ple and &uic+ )irror chan'e *ith a s&uare bea) profile. Alu)iniu)3 free, 'as3te)perature controlled *ith no condensin' due to coolin' *ater. Ther)ally stable laser resonator5 stable laser output po*er independent of pulse fre&uency and operatin' ti)e.The electrical specs are 1=832/0 O, 803/0 @$, 1 !h, 1.8 +W. The laser uses a 8 co)ponent )i( of 'as *hich can be bou'ht co))ercially and can differ dependin' on the application. Ior detonation of 12 to ato)ic o(y'en in its lo*est ato)ic state #triplet !% the an order fro) 7eneral Distributin' for an alu)inu) hi'h pressure tan+ 2200 psi' W 00oC *ith a )i(ture loo+s li+e this5 0.3X @ydro'en 3 Research 7rade, <.0X Carbon Mono(ide 3 Research 7rade, A.0X Carbon Dio(ide 3 Research 7rade, 1=.0X .itro'en 3 Research 7rade. 2alance @eliu) 3 Research 7rade. The laserDs consu)ption is a 80 liter bottle for a )ini)u) 2 years if operated 3/8 days a year. This *ill -ary in a research settin' dependin' on ho* often the laser is pur'ed *ith ne* 'as since it is not operated continuously. ye safety is of 'reat concern *ith all lasers includin' this C12 laser especially because it produced an in-isible bea) of li'ht and is operated in the line of si'htG it is a Class < laser product. The laser is bein' fired into a -acuu) cha)ber that is pu)ped by a diffusion pu)p usin' ;anto-ac 8 #polyphenyl ether% *ith a che-ron li&uid nitro'en cooled baffle. The diffusion pu)p is bac+ed *ith an Alcatel 2033 dual sta'e rotary -ane pu)p that uses Io)blin or Qryto( #perfluorinated polyether oil%, )anufactured by Ausi)ont and Du!ont respecti-ely. These special oils are used because they are pri)arily pu)pin' o(y'en *hich *ould o(idi$e and destroy hydrocarbon oils and thus the pu)ps the)sel-es. http599***.2spi.co)9catalo'9-ac9-ac3fluids1.sht)l
in @.
The C12 laser bea) tra-els throu'h a 3 inch dia)eter anti3reflecti-e coated $inc selenide *indo* )ounted in a flan'e to separate the -acuu) en-iron)ent fro) the at)osphere. The anti3reflecti-e coatin' is added to )ini)i$e loss due to reflection because Yn;e has a hi'h inde( of refraction #2.<02= W 10./ J)%. The AR coatin' reflecti-ity at 10./J) is less than 0.20X. "nde( -ariations *ill test to less than 3 pp) at 0./32= )icrons re'ardless of orientation. The )aterial used as a AR coatin' *as not )entioned on any of the suppliers *ebsite ho*e-er ;an+ur and ;outh*ell desi'ned, fabricated and tested an AR coatin' 1A=< by laser3aided e-aporation of a binary co)pound syste) Yn;e5CaI2. ;an+ur and W. @. ;outh*ell, E2roadband 7radient3"nde(
Antireflection Coatin' for Yn;e,E Appl. 1pt. 23, 2000 #1A=<%. Yn;e ha-in' a lar'e Rupture Modulus Z =,000 psi and 6oun'Ds Modulus Z /0.2 7!a #A.08 ( 10/ psi%, only recei-in' about 180 psi separatin' -acuu) #0psi% fro) at)osphere #18psi% *ith a linear e(pansion coefficient W 20[ C Z 0.80 ( 103/9[C it )a+es a 'reat )aterial for *indo* on -acuu) cha)bers needin' an entrance for infrared li'ht. The *indo* has a da)a'e threshold of 8 ?9c)2 W 10./ J), 100 ns, 1 @$, \0.<0= )). Yn;e is also not hy'roscopic unli+e )any salts *hich are used for *indo*s in the infrared. The do*nside to the )aterial is its Qnoop @ardness Z 1083120 +'9))2 *hich is only sli'htly hi'her than 'old or around 1.8 on the Mohs harness scale. The proble) *ith usin' a T A C12 laser *ithout focusin' the bea) before enterin' the cha)ber is a 3 inch dia)eter *indo* is needed *hich is si'nificantly )ore e(pensi-e than a 2 inch *indo* for )any reasons includin' the difficulty to 'ro* a 3 inch dia)eter Yn;e crystal. http599***.ii-iinfrared.co)91ptical3Materials9$nse.ht)l
7old Mirror The 08 )) dia)eter 'old3coated conca-e )irror inside the cha)ber is also essential to the detonation of the o(y'en. The )irror has a 1000)) radius of cur-ature thus a focal len'th of 800)). This 'i-es sufficient distance fro) the pulse of o(y'en *hile still +eepin' the incidence and reflectance an'le s)all and the )irror out of the path of the o(y'en bea). "t see)s a s)aller )irror *ould *or+ by chan'in' the an'le of incidence and position a*ay fro) the o(y'en bea) ho*e-er this is not possible because of the conical copper no$$le in *hich the t*o bea)s )ust collide. The 'old )irror has the hi'hest reflectance in the infrared and thus the
best choice for this application. "t has ]A/X A-era'e Reflecti-ity5 =00 n) 3 20 J) and a da)a'e threshold5 2.0 ?9c)2 at 10/< n), 10 ns, 10 @$, \1.000 ))