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PHYSICS: SMYTH AND BRASEFIELD

TIHE SECONDARY SPECTRUM OF HYDROGEN AND THE


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
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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
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f f -
F
V oi. 1 2 , 1 9 2 6 4 4 5
Im
r a 0 /V IL 1 7
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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