OCCURRENCE OF f I3 + By H. D. SMYTH AND C. J . BRASBr IELD PALMZR PHYSICAL LABORATORY, PRINCETON Communicated May 3 1 , 1 9 2 6 Intr oduction. - In s p ite of th e al mos t innumer ab l e s tudies w h ich h av e b een made of th e s econdar y or many l ined s p ectr um of h ydr og en its de- tail ed ex p l anation r emains f ar f r om comp l ete. Th e p r ob l em is th e' mor e f as cinating b ecaus e it inv ol v es th e s tr uctur e of th e h ydr og en mol ecul e and its s ol ution mus t h av e an imp or tant b ear ing on th e w h ol e q ues tion of mol ecul ar s tr uctur e. Th e r ecent w or k of Dieke, l W itmer and oth er s indicates incr eas ing l y r ap id p r og r es s on th e th eor etical s ide of th e p r ob l em and s ug g es ts to th e w r iter s th at a p r el iminar y r ep or t on cer tain ex p er i- mental w or k may not b e out of p l ace. Pos itiv e r ay anal ys is of th e p r oducts of ioniz ation in h ydr og en s h ow s th at under p r op er conditions H3 + ions ar e f ar mor e numer ous th an H2 + ions . 2 Pr omp ted b y th is r es ul t th e w r iter s h av e b een attemp ting to dis cov er w h eth er or not any p ar t of th e s econdar y s p ectr um mig h t b e attr ib uted to H3 or H3 + . Such a p os s ib il ity h as b een dis cus s ed in connection w ith s ome of th e attemp ts to ar r ang e th e l ines in s er ies b ut h as not, w e b el iev e, b een s ub j ected to ex p er imental s cr utiny. Th e f ir s t meth od us ed w as dir ect and s imp l y inter p r eted b ut unf or tu- natel y p r oduced no r es ul ts . It w as anal og ous to th e ex p er iments of G. P. Th oms on, 3 dep ending on th e dir ect ob s er v ation of th e s p ectr um of a h omo- g eneous b eam of H3 + ions p as s ing into an el ectr on atmos p h er e. As h ad b een f ear ed, th e amount of l ig h t p r oduced p r ov ed too s mal l to b e p h oto- g r ap h ed. Th e s econd meth od, now in us e, cons is ts of th e cor r el ation of s p ectr os cop ic and p os itiv e ion concentr ation meas ur ements in a g l ow dis - ch ar g e in h ydr og en. Such a meth od is s ug g es tiv e r ath er th an concl us iv e. Th us , if p os itiv e r ay meas ur ements s h ow th at under cer tain conditions th e r atio of H3 + to H2 + is v er y g r eat and a s imul taneous p h otog r ap h s h ow s cer tain l ines in th e s econdar y s p ectr um accentuated, it does not neces s ar il y f ol l ow th at th es e l ines ar e due to H3 + . W e can onl y s ay th at th e conditions w h ich f av or th e p r oduction of H3 + f av or th e ex citation of th es e l ines . How ev er , ev en th is may b e of s ome v al ue, s o w e w il l p r oceed to a dis cus s ion of th e ap p ar atus and th e r es ul ts th us f ar ob tained. Ap p ar atus and Pr ocedur e. - Hydr og en is g ener ated el ectr ol ytical l y f r om a s ol ution of b ar ium h ydr ox ide, s tor ed ov er p h os p h or ous p entox ide, f ur th er p ur if ied b y cocoanut ch ar coal immer s ed in l iq uid air and f inal l y p as s ed into th e dis ch ar g e tub e continual l y th r oug h a cap il l ar y l eak. ' Th e dis - ch ar g e tub e is 1 . 5 inch es in diameter w ith a tung s ten f il ament cath ode and V OL. 1 2 , 1 9 2 6 4 4 3 PHYSICS: SMYTH AND BRASEFIELD nickel p l ate anode ab out 1 5 cms . ap ar t. Th e f ix ed el ectr odes us ed at f ir s t w er e af ter w ar ds r ep l aced b y th e mov ab l e s ys tem us ed b y McCur dy and Dal ton. 4 Th e v ol tag es acr os s th e tub e ar e of th e or der of 8 0 to 1 8 0 v ol ts and th e cur r ents maintained of th e or der of 5 0 to 1 5 0 mil l iamp er es . As s h ow n in f ig ur e 1 , th e dev ice f or meas ur ing r el ativ e concentr ations of dif f er ent kinds of p os itiv e ions is l et into th e s ide of th e dis ch ar g e tub e, b etw een th e cath ode and anode. It is of th e s ame g ener al typ e des cr ib ed b ef or e b y one of us , 2 th oug h th er e ar e a f ew minor modif i- cations as may b e s een f r om . tJ s ch ar e th e dr aw ing . Th e el ectr ode, l iu6 e ~ Si, is kep t at s uch a p otential ( us ual l y th at of th e cath ode) th at p os itiv e ions ar e dr aw n to dech ' ometer tow ar d it. Enter ing th e s l it Si w ith s ome initial v el ocity th ey ar e f ur th er accel er ated b y a v ar iab l e f iel d V b etw een Si and S2 , th en b ent in a s emi- cir cl e b y th e mag netic f iel d and r each th e Far aday cyl inder ittoPUMP connected to a Comp ton el ec- tr ometer . W ith cons tant con- ditions in th e dis ch ar g e tub e and cons tant mag netic f iel d FIGURE I th e cur r ent r each ing th e el ec- tr ometer is ob s er v ed as a f unc- tion of th e el ectr ic f iel d V . Th e r es ul tant cur v e ( e. g . , Fig . 2 ) th en g iv es th e r el ativ e concentr ations of H1 + , H2 + and H3 + . Simul taneous l y a p h oto- g r ap h is taken w ith a cons tant dev iation s p ectr og r ap h , th e s l it b eing dir ected at th e r eg ion of th e dis ch ar g e immediatel y ab ov e th e el ectr ode Sl of th e p os itiv e- r ay s ys tem. Res ul ts . - In or der to deter mine th e conditions of th e dis ch ar g e under w h ich th e r atio of H3 + to H2 + w as g r eates t and s mal l es t, r es p ectiv el y, a l ar g e numb er of p os itiv e- r ay meas ur ements w er e made b ef or e any s p ectr a w er e p h otog r ap h ed. It w as f ound th at th e v ar iation of cur r ent dens ity, v ol tag e acr os s th e tub e, p ar t of th e dis ch ar g e ov er Sl , etc. , al l h ad s mal l ef f ect comp ar ed to th at of v ar iation of p r es s ur e. Tw o cur v es , one taken at a h ig h and one at a f air l y l ow p r es s ur e ar e s h ow n in f ig ur e 2 . Th ey ar e s een to b e s imil ar to th os e taken in ear l ier ex p er iments under dif f er ent conditions of ioniz ation and s h ow th at th e dis ch ar g e can b e maintained ov er a v er y w ide r ang e of v ar iation of th e r atio of H3 + to H2 + . Th e ob - j ect of th e p r el iminar y p os itiv e- r ay inv es tig ation w as th er ef or e ach iev ed 4 4 4 PROC. N. A. S. PHYSICS: SMYTH AND BRASEFIELD and w h il e a numb er of oth er inter es ting p oints w er e s ug g es ted b y it th eir cons ider ation w il l b e p os tp oned. Ear l y s p ectr os cop ic ob s er v ations s h ow ed th e Bal mer l ines , th e s econdar y s p ectr um, and s ome of th e s tr ong er l ines of mer cur y. Th e l atter g r adual l y dis ap p ear ed af ter l iq uid air h ad b een kep t on th e tr ap s continual l y f or ov er tw o w eeks and th ey h ad b een too w eak to ob s er v e f or s ev er al w eeks b ef or e th e f inal p h otog r ap h s w er e taken. Incidental l y, it is inter es ting th at th e r el ativ e concentr ation of H- + dr op p ed of f cons ider ab l y at th e s ame time, as mig h t b e ex p ected f r om th e ces s ation of col l is ions of th e s econd AI I Ii. - - - I; - - - - I b Ig - __- 1 2 4 . L. I T _it I "k1 h J 6 IC . 0 5 5 SA I X I . ___- ' I - - - - ' Cr I 1 i J t Ic Q I= l - a I - & - ' - - , - A - . - ' U FIGURE 2 kind b etw een ex cited mer cur y atoms and h ydr og en mol ecul es . Anoth er s p ectr os cop ic imp ur ity th at dev el op ed l ater w as th e comet tail b ands ' f r om CO+ r es ul ting ap p ar entl y f r om th e ov er h eating of th e de K h otins ky cement j oint of th e p os itiv e- r ay b ox to th e dis ch ar g e tub e. Th is w as p ar ticul ar l y tr oub l es ome at l ow p r es s ur es b ut w as f inal l y al mos t comp l etel y el iminated b y p utting w ater cool ing on th e j oint and r unning th e tub e f or s ev er al h our s b ef or e taking a p h otog r ap h . Unf or tunatel y th e el imination of h eav y s p ace- ch ar g e des tr oying imp ur ities made it imp os s ib l e to r un 4 L _i 6 f f - F V oi. 1 2 , 1 9 2 6 4 4 5 Im r a 0 /V IL 1 7 V v 4 I OC V I yy Ye PHYSICS: SMYTH AND BRASEFIELD th e dis ch ar g e at s uf f icientl y l ow p r es s ur es to r educe th e r atio of H3 + to H2 + much b el ow one. How ev er , p h otog r ap h s w er e taken w h ich s h ow ed q ual itativ el y a s tr eng th - ening of th e Ful ch er b ands r el ativ e to th e r es t of th e s econdar y s p ectr um at th e h ig h er p r es s ur es w h ich f av or H3 + . Final l y b y taking an ex p os ur e of 3 h r s . at a p r es s ur e of 0 . 0 1 2 mm. and h al f an h our at a p r es s ur e of 0 . 1 3 mm. tw o s p ectr a w er e ob tained on th e s ame p l ate w ith v er y near l y th e s ame intens ity of th e Ful ch er l ines b ut w ith mos t of th e s p ectr um much w eaker in th e h ig h p r es s ur e, s h or t ex p os ur e p ictur e. Th e p os ition of ev er y l ine in each s p ectr um w as th en meas ur ed and its intens ity es timated. Th e w av e l eng th s w er e th en cal cul ated, ch ecked ag ains t a cop p er comp ar is on s p ectr um on th e s ame p l ate, and comp ar ed w ith th os e of Mer ton and Bar - r att. 6 Th e meas ur ements w er e f ound s uf f icientl y accur ate to identif y th e l ines ex cep t in a f ew cas es . Th e es timated intens ities of th e l ines in th e tw o s p ectr a w er e th en comp ar ed. Of th e 3 5 0 to 4 0 0 l ines meas ur ab l e al l b ut ab out 75 w er e w eaker on th e h ig h p r es s ur e, s h or t ex p os ur e p h otog r ap h and cons eq uentl y th e l ines w h ich w er e s tr ong er or eq ual l y s tr ong at h ig h p r es s ur es w il l b e r ef er r ed to as l ines f av or ed b y h ig h p r es s ur e. Th e maj or ity of th es e l ines w er e to b e f ound in Dieke' s tab l es of th e Ful ch er l ines accor ding to h is ex tens ions and r ear r ang ements . Th er e w as al s o a g r oup of tw el v e l ines in th e v iol et, X 4 4 1 0 . 6 to X 4 4 6 1 . 0 , a l ar g er g r oup of ab out eig h teen in th e yel l ow , X 5 72 8 . 5 to X 5 9 70 , and p er h ap s h al f a doz en s catter ed th r oug h th e s p ec- tr um, in al l , ab out tw enty- f iv e uncl as s if ied l ines , w h ich ap p ear ed to b eh av e in th e s ame w ay as th e l ines of th e Dieke- Ful ch er cl as s if ication. In th e v ar iation of intens ity of th e cl as s if ied l ines th er e s eem to b e cer - tain r eg ul ar ities . Th us , al l th e l ines ( b oth z er o and p os itiv e b r anch es ) of th e r ed g r oup ( Dieke, Tab l e 1 ) ar e r el ativ el y s tr ong er at h ig h p r es s ur e, b ut in th e g r een g r oup th e ef f ect is not s o mar ked and s til l l es s s o in th e b l ue g r oup . Fur th er , in th e g r een g r oup th e l ines m = 1 in each s ub - g r oup ar e much mor e enh anced at h ig h p r es s ur es th an th e l ines of h ig h er r otational q uantum numb er . It is p os s ib l e th at th is ef f ect is p r es ent in th e r ed and b l ue g r oup s al s o b ut it is cer tainl y much l es s ob v ious . It is not our intention in th is p ap er to attemp t a detail ed ex p l anation of th es e r es ul ts or a dis cus s ion of th eir b ear ing on th os e of p r ev ious w or ker s . How ev er , w e f eel th at th e ev idence ob tained does l ead to th e concl us ion th at conditions of - dis ch ar g e w h ich f av or th e p r oduction of H3 + f av or th e ex citation of th e Ful ch er b ands , p ar ticul ar l y th os e in th e r ed. W e h op e th at th is b it of ev idence may b e of s er v ice to th os e w or king in th is f iel d and th at w e may b e ab l e to add mor e b y f ur th er ex p er iments . 1 Dieke, G. H. , Pr oc. Roy. Acad. Ams ter dam, 2 7, p p . 4 9 0 - 5 0 0 , 1 9 2 4 ; Dieke, G. H. , Ph il . Mag . , 5 0 , p p . 1 73 - 1 8 0 , J ul y, 1 9 2 5 ; Dieke, G. H. , Zs . Ph ys ik, 3 2 , p . 1 8 0 , 1 9 2 5 ; W itmer , E. E. , Pr oc. Nat. Acad. Sci. , 1 2 , p p . 2 3 8 - 2 4 4 , Ap r il , 1 9 2 6 ; Bur y, C. R. , Ph il . 4 4 6 PROCe. N. A. S. PHYSICS: GIDDINGS AND ROUSE Mag . , 5 0 , 1 1 3 9 - 1 1 4 3 , Nov . , 1 9 2 5 ; Rich ar ds on, 0 . W . , and Tanaka, T. , Pr oc. Roy. Soc. , 1 0 6 , p p . 6 6 3 - 6 78 , 1 9 2 4 , and s ub s eq uentl y. 2 Demp s ter , A. J . , Ph il . Mag . , 3 1 , p p . 4 3 8 - 4 4 3 , 1 9 1 6 ; Smyth , Ph ys ic. Rev . , 2 5 , p p . 4 5 2 - 4 6 8 , 1 9 2 5 ; Hog nes s and Lunn, Ph ys ic. Rev . , 2 6 , p . 4 4 , 1 9 2 5 . Th oms on, G. P. , Ph il . Mag . , 4 0 , p p . 2 4 0 - 2 4 6 , 1 9 2 0 . 4 McCur dy and Dal ton, Ph ys ic. Rev . , 2 7, p . 1 6 5 , Feb . , 1 9 2 6 . 6 A p os itiv e- r ay meas ur ement indicated th e p r es ence of CO+ ions w h en th es e b ands w er e s tr ong conf ir ming th e now g ener al l y accep ted v iew of th eir or ig in. 6 Mer ton and Bar r att, Ph il . Tr ans . , A, 2 2 2 , p p . 3 6 9 - 4 0 0 , 1 9 2 2 . IONIZATION OF MERCURY V APOR AS A FUNCTION OF THE INTENSITY OF EX CITING LIGHT By G. W . GIDDINGS AND G. F. Rous il UNIV ERSITY OF W ISCONSIN Communicated J une 1 6 , 1 9 2 6 In a p r ev ious p ap er ( th es e PROCEEDINGS, 1 1 , 1 9 2 5 , p p . 5 1 4 - 5 1 7) th e auth or s r ep or ted an inv es tig ation in w h ich it w as f ound th at mer cur y v ap or can b e ioniz ed b y l ig h t f r om a w ater cool ed q uar tz mer cur y ar c, and in p ar ticul ar th at ioniz ation may b e p r oduced b y l ig h t of w av e- l eng th 2 5 3 6 A. al one. Th e w or k h as b een continued and a s tudy made of th e v ar iation of ioniz ation as a f unction of th e intens ity of th e ex citing l ig h t. Th e ex p er imental ar r ang ements ar e es s ential l y as p r ev ious l y des cr ib ed ex cep t th at a s l iding s il v er mir r or h as b een p l aced b etw een th e s p ectr om- eter and th e tub e s o th at th e l ig h t f r om th e s p ectr ometer may b e r ef l ected into a p otas s ium p h oto- el ectr ic cel l f or intens ity meas ur ements . Mono- ch r omatic l ig h t of w av e- l eng th 2 5 3 6 A. is us ed. Th e intens ity of th e l ig h t is v ar ied b y p l acing f us ed q uar tz p l ates in th e p ath of th e b eam b etw een th e ar c and th e s p ectr ometer , and meas ur ements ar e taken of th e ioniz ation cur r ent and of th e r el ativ e intens ities of th e ex citing l ig h t. For mos t of th e ob s er v ations onl y tw o intens ities h av e b een us ed, s ince it w as f ound th at f or any g iv en s et of conditions , th e ioniz ation cur r ent is s ens ib l y th e s ame f unction of th e l ig h t intens ity, indep endent of th e actual v al ue of th e intens ity. Dur ing ob s er v ations th e tub e is cut of f f r om th e p ump ing s v s tem b y a mer cur y s h ut- of f ins ide th e f ur naces . Th e ioniz ation cur r ent as a f unction of th e l ig h t intens ity is comp uted f r om th e eq uation Co/Cl = ( Io/I0 ) t w h er e CO and C1 r ep r es ent th e or ig inal and r educed ioniz ation cur r ents and Io and I, r ep r es ent th e cor r es p onding l ig h t intens ities . Th e v ar iation of n as a f unction of v ap or p r es s ur e and of temp er atur e is b eing inv es tig ated and s ome p r el iminar y r es ul ts h av e b een ob tained. V oi, . 1 2 , 1 9 2 6 4 4 7