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»74 

Tfe. 


UC-NRLF 


B   M   ES3   D7D 


THE  ORIGIN  AND  DEVELOPMENT 

OF  THE 


QUANTUM  THEORY 


BY 


MAX    PLANCK 


TRANSLATED  BY 


H.  T.  CLARKE  AND  L,  SILBERSTEIN 


BEING   THE 


NOBEL    PRIZE    ADDRESS 


DELIVERED    BEFORE 


THE    ROYAL   SWEDISH   ACADEMY   OF   SCIENCES 
AT    STOCKHOLM,  2  JUNE,   1920 


OXFORD 
AT   THE   CLARENDON  PRESS 

1922 


THE  ORIGIN  AND  DEVELOPMENT 

OF  THE 

,    *     J    >  J 

QUANTUM  THEORY 

BY 

MAX   PLANCK 


TRANSLATED  BY 


H.  T.  CLARKE  AND  L.  SILBERSTEIN 


BEING  THE 


NOBEL    PRIZE    ADDRESS 


DELIVERED    BEFORE 


THE    ROYAL   SWEDISH   ACADEMY   OF   SCIENCES 
AT   STOCKHOLM,  2  JUNE,  1920 


OXFORD 

AT   THE   CLARENDON  PRESS 
1922 


OXFORD  UNIVERSITY  PRESS 

London       Edinburgh      Glasgow      Copenhagen 

New  York    Toronto    Melbourne    Cape  Town 

Bombay     Calcutta     Madras     Shanghai 

HUMPHREY  MILFORD 

Publisher  to  the  University 


THE  ORIGIN  AND  DEVELOPMENT  OF 
THE  QUANTUM  THEORY 

MY  task  this  day  is  to  present  an  address  dealing  with 
the  subjects  of  my  publications.  I  feel  I  can  best  dis- 
charge this  duty,  the  significance  of  which  is  deeply 
impressed  upon  me  by  my  debt  of  gratitude  to  the 
generous  founder  of  this  Institute,  by  attempting  to  sketch 
in  outline  the  history  of  the  origin  of  the  Quantum  Theory 
and  to  give  a  brief  account  of  the  development  of  this  theory 
and  its  influence  on  the  Physics  of  the  present  day. 

When  I  recall  the  days  of  twenty  years  ago,  when  the 
conception  of  the  physical  quantum  of  '  action '  was  first 
beginning  to  disentangle  itself  from  the  surrounding  mass 
of  available  experimental  facts,  and  when  I  look  back  upon 
the  long  and  tortuous  road  which  finally  led  to  its  disclosure, 
this  development  strikes  me  at  times  as  a  new  illustration 
of  Goethe's  saying,  that  'man  errs,  so  long  as  he  is  striving '. 
And  all  the  mental  effort  of  an  assiduous  investigator  must 
$  indeed  appear  vain  and  hopeless,  if  he  does  not  occasionally 
run  across  striking  facts  which  form  incontrovertible  proof 
of  the  truth  he  seeks,  and  show  him  that  after  all  he  has 
moved  at .  least  one  step  nearer  to  his  objective.  The 
pursuit  o*f  a  goal,  the  brightness  of  which  is  undimmed  by 
initial  failure,  is  an  indispensable  condition,  though  by  no 
means  a  guarantee,  of  final  success. 

In  my  own  case  such  a  goal  has  been  for  many  years 
the  solution  of  the  question  of  the  distribution  of  energy  in 
the  normal  spectrum  of  radiant  heat.  The  discovery  by 
Gustav  Kirchhoff  that  the  quality  of  the  heat  radia- 
tion produced  in  an  enclosure  surrounded  by  any 

A  2 


717303 


emitting  or  absorbing  bodies  whatsoever,  all  at  the  same 
temperature,  is  entirely  independent  of  the  nature  of  such 
bodies  (I)1,  established  the  existence  of  a  universal  function, 
which  depends  only  upon  the  temperature  and  the  wave- 
length, and  is  entirely  independent  of  the  particular  pro- 
perties of  the  substance.  And  the  discovery  of  this  re- 
markable function  promised  a  deeper  insight  into  the  relation 
between  energy  and  temperature,  which  is  the  principal 
problem  of  thermodynamics  and  therefore  also  of  the 
entire  field  of  molecular  physics.  The  only  road  to  this 
function  was  to  search  among  all  the  different  bodies 
occurring  in  nature,  to  select  one  of  which  the  emissive  and 
absorptive  powers  were  known,  and  to  calculate  the  energy 
distribution  in  the  heat  radiation  in  equilibrium  with  that 
body.  This  distribution  should  then,  according  to  KirchhofFs 
law,  be  independent  of  the  nature  of  the  body. 

A  most  suitable  body  for  this  purpose  seemed  H.  Hertz's 
rectilinear  oscillator  (dipole)  whose  laws  of  emission  for  a 
given  frequency  he  had  just  then  fully  developed  (2).     If 
a  number  of  such  oscillators  be  distributed  in  an  enclosure 
surrounded  by  reflecting  walls,  there  would  take  place,  in  * 
analogy  with  sources  and  resonators  in  the  cas*  * e. sound,  •    w 
an  exchange   of  energy  by   means   of  the  S^Mf*1  ana     U> 
reception  of  electro-magnetic  wavee^  -and  finJ^jEjfeat   is 
known  as  black  body  radiation  corresponding  td*&ffchhoff  s 
law  should  establish  itself  in  the  vacuum-enclosure.     I  ex- 
pected, in  a  way  which  certainly  seems  at  the  present  day 
somewhat  naive,  that  the  laws  of  classical  electrodynamics 
would  suffice,  if  one  adhered  sufficiently  to  generalities  and 
avoided  too  special  hypotheses,  to  account  in  the  main  for 

1  The  numbers  in  brackets  refer  to  the  notes  at  the  end  of  the 
article. 


(5) 

the  expected  phenomena  and  thus  lead  to  the  desired  goal. 
I  thus  first  developed  in  as  general  terms  as  possible  the 
laws  of  the  emission  and  absorption  of  a  linear  resonator, 
as  a  matter  of  fact  by  a  rather  circuitous  route  which  might 
have  been  avoided  had  I  used  the  electron  theory  which 
had  just  been  put  forward  by  H.  A.  Lorentz.  But  as  I  had 
not  yet  complete  confidence  in  that  theory  I  preferred  to 
consider  the  energy  radiating  from  and  into  a  spherical 
surface  of  a  suitably  large  radius  drawn  around  the 
resonator.  In  this  connexion  we  need  to  consider  only 
processes  in  an  absolute  vacuum,  the  knowledge  of  which, 
however,  is  all  that  is  required  to  draw  the  necessary  con- 
clusions concerning  the  energy  changes  of  the  resonator. 

• 

The  outcome  of  this  long  series  of  investigations,  of 
which  some  could  be  tested  and  were  verified  by  com- 
parison with  existing  observations,  e.  g.  the  measurements 
of  V.  Bjerknes(3)  on  damping,  was  the  establishment  of 
a  general  relation  between  the  energy  of  a  resonator  of 
a  definite  free  frequency  and  the  energy  radiation 
of  the  corresponding  spectral  region  in  the  surrounding 
field  in  equilibrium  with  it  (4).  The  remarkable  result 
was  obtained  that  this  relation  is  independent  of  the 
nature  of  the  resonator,  and  in  particular  of  its  coefficient 
of  damping — a  result  which  was  particularly  welcome, 
since  it  introduced  the  simplification  that  the  energy  of  the 
radiation  could  be  replaced  by  the  energy  of  the  resonator, 
so  that  a  simple  system  of  one  degree  of  freedom  could  be 
substituted  for  a  complicated  system  having  many  degrees 
of  freedom. 

But  this  result  constituted  only  a  preparatory  advance 
towards  the  attack  on  the  main  problem,  which  now 
towered  up  in  all  its  imposing  height.  The  first  attempt  to 


master  it  failed :  for  my  original  hope  that  the  radiation 
emitted  by  the  resonator  would  differ  in  some  characteristic 
way  from  the  absorbed  radiation,  and  thus  afford  the 
possibility  of  applying  a  differential  equation,  by  the  integra- 
tion of  which  a  particular  condition  for  the  composition  of 
the  stationary  radiation  could  be  reached,  was  not  realized. 
The  resonator  reacted  only  to  those  rays  which  were  emitted 
by  itself,  and  exhibited  no  trace  of  resonance  to  neighbour- 
ing spectral  regions. 

Moreover,  my  suggestion  that  the  resonator  might  be 
able  to  exert  a  one-sided,  i.  e.  irreversible,  action  on  the 
energy  of  the  surrounding  radiation  field  called  forth  the 
emphatic  protest  of  Ludwig  Boltzmann  (5),  who  with  his 
more  mature  experience  in  these  questions  succeeded  in 
showing  that  according  to  the  laws  of  the  classical 
dynamics  every  one  of  the  processes  I  was  considering 
could  take  place  in  exactly  the  opposite  sense.  Thus 
a  spherical  wave  emitted  from  a  resonator  when  reversed 
shrinks  in  concentric  spherical  surfaces  of  continually  de- 
creasing size  on  to  the  resonator,  is  absorbed  by  it,  and  so 
permits  the  resonator  to  send  out  again  into  space  the 
energy  formerly  absorbed  in  the  direction  from  which  it 
came.  And  although  I  was  able  to  exclude  such  singular 
processes  as  inwardly  directed  spherical  waves  by  the 
introduction  of  a  special  restriction,  to  wit  the  hypothesis 
of  '  natural  radiation ',  yet  in  the  course  of  these  investiga- 
tions it  became  more  and  more  evident  that  in  the  chain 
of  argument  an  essential  link  was  missing  which  should 
lead  to  the  comprehension  of  the  nature  of  the  entire 
question. 

The  only  way  out  of  the  difficulty  was  to  attack  the 
problem  from  the  opposite  side,  from  the  standpoint  of 


(7) 

thermodynamics,  a  domain  in  which  I  felt  more  at  home. 
And  as  a  matter  of  fact  my  previous  studies  on  the  second 
law  of  thermodynamics  served  me  here  in  good  stead,  in 
that  my  first  impulse  was  to  bring  not  the  temperature  but 
the  entropy  of  the  resonator  into  relation  with  its  energy, 
more  accurately  not  the  entropy  itself  but  its  second 
derivative  with  respect  to  the  energy,  for  it  is  this 
differential  coefficient  that  has  a  direct  physical  significance 
for  the  irreversibility  of  the  exchange  of  energy  between 
the  resonator  and  the  radiation.  But  as  I  was  at  that  time 
too  much  devoted  to  pure  phenomenology  to  inquire  more 
closely  into  the  relation  between  entropy  and  probability, 
I  felt  compelled  to  limit  myself  to  the  available  ex- 
perimental results.  Now,  at  that  time,  in  1899,  interest 
was  centred  on  the  law  of  the  distribution  of  energy, 
which  had  not  long  before  been  proposed  by  W.  Wien  (6), 
the  experimental  verification  of  which  had  been  under- 
taken by  F.  Paschen  in  Hanover  and  by  0.  Lummer  and 
E.  Pringsheim  of  the  Reichsanstalt,  Charlottenburg.  This 
law  expresses  the  intensity  of  radiation  in  terms  of  the 
temperature  by  means  of  an  exponential  function.  On 
calculating  the  relation  following  from  this  law  between 
the  entropy  and  energy  of  a  resonator  the  remarkable 
result  is  obtained  that  the  reciprocal  value  of  the  above 
differential  coefficient,  which  I  shall  here  denote  by  J?,  is 
proportional  to  the  energy  (7).  This  extremely  simple 
relation  can  be  regarded  as  an  adequate  expression  of 
Wien's  law  of  the  distribution  of  energy  ;  for  with  the  de- 
pendence on  the  energy  that  of  the  wave-length  is  always 
directly  given  by  the  well-established  displacement  law  of 
Wien  (8). 

Since  this  whole  problem  deals  with  a  universal  law  of 


(8) 

nature,  and  since  I  was  then,  as  to-day,  pervaded  with 
a  view  that  the  more  general  and  natural  a  law  is  the 
simpler  it  is  (although  the  question  as  to  which  formulation 
is  to  be  regarded  as  the  simpler  cannot  always  be  definitely 
and  unambiguously  decided),  I  believed  for  the  time  that 
the  basis  of  the  law  of  the  distribution  of  energy  could 
be  expressed  by  the  theorem  that  the  value  of  E  is  pro- 
portional to  the  energy  (9).  But  in  view  of  the  results 
of  new  measurements  this  conception  soon  proved  un- 
tenable. For  while  Wien's  law  was  completely  satisfactory 
for  small  values  of  energy  and  for  short  waves,  on  the  one 
hand  it  was  shown  by  0.  Lummer  and  E.  Pringsheim 
that  considerable  deviations  were  obtained  with  longer 
waves  (10),  and  on  the  other  hand  the  measurements  carried 
out  by  H.  Eubens  and  F.  Kurlbaum  with  the  infra-red 
residual  rays  (Eeststrahlen)  of  fluorspar  and  rock  salt  (11) 
disclosed  a  totally  different,  but,  under  certain  circum- 
stances, a  very  simple  relation  characterized  by  the  pro- 
portionality of  the  value  of  E  not  to  the  energy  but  to  the 
square  of  the  energy.  The  longer  the  waves  and  the  greater 
the  energy  (12)  the  more  accurately  did  this  relation  hold. 

Thus  two  simple  limits  were  established  by  direct 
observation  for  the  function  E :  for  small  energies  propor- 
tionality to  the  energy,  for  large  energies  proportionality  to 
the  square  of  the  energy.  Nothing  therefore  seemed 
simpler  than  to  put  in  the  general  case  E  equal  to  the  sum 
of  a  term  proportional  to  the  first  power  and  another 
proportional  to  the  square  of  the  energy,  so  that  the  first 
term  is  relevant  for  small  energies  and  the  second  for  large 
energies  ;  and  thus  was  found  a  new  radiation  formula  (13) 
which  up  to  the  present  has  withstood  experimental 
examination  fairly  satisfactorily.  Nevertheless  it  cannot 


(9) 

be  regarded  as  having  been  experimentally  confirmed  with 
final  accuracy,  and  a  renewed  test  would  be  most 
desirable  (14). 

But  even  if  this  radiation  formula  should  prove  to  be 
absolutely  accurate  it  would  after  all  be  only  an  interpola- 
tion formula  found  by  happy  guesswork,  and  would  thus 
leave  one  rather  unsatisfied.  I  was,  therefore,  from  the 
day  of  its  origination,  occupied  with  the  task  of  giving  it 
a  real  physical  meaning,  and  this  question  led  me,  along 
Boltzmann's  line  of  thought,  to  the  consideration  of  the 
relation  between  entropy  and  probability ;  until  after  some 
weeks  of  the  most  intense  work  of  my  life  clearness  began 
to  dawn  upon  me,  and  an  unexpected  view  revealed  itself 
in  the  distance. 

Let  me  here  make  a  small  digression.  Entropy, 
according  to  Boltzmann,  is  a  measure  of  a  physical  prob- 
ability, and  the  meaning  of  the  second  law  of  thermo- 
dynamics is  that  the  more  probable  a  state  is,  the  more 
frequently  will  it  occur  in  nature.  Now  what  one  measures 
are  only  the  differences  of  entropy,  and  never  entropy 
itself,  and  consequently  one  cannot  speak,  in  a  definite 
way,  of  the  absolute  entropy  of  a  state.  But  nevertheless 
the  introduction  of  an  appropriately  defined  absolute 
magnitude  of  entropy  is  to  be  recommended,  for  the  reason 
that  by  its  help  certain  general  laws  can  be  formulated 
with  great  simplicity.  As  far  as  I  can  see  the  case  is  here 
the  same  as  with  energy.  Energy,  too,  cannot  itself  be 
measured  ;  only  its  differences  can.  In  fact,  the  concept 
used  by  our  predecessors  was  not  energy  but  work,  and 
even  Ernst  Mach,  who  devoted  much  attention  to  the  law 
of  conservation  of  energy  but  at  the  same  time  strictly 
avoided  all  speculations  exceeding  the  limits  of  observation, 

A  8 


(10) 

always  abstained  from  speaking  of  energy  itself.  Similarly 
in  the  early  days  of  thermochemistry  one  was  content  to 
deal  with  heats  of  reaction,  that  is  to  say  again  with 
differences  of  energy,  until  Wilhelm  Ostwald  emphasized 
that  many  complicated  calculations  could  be  materially 
shortened  if  energies  instead  of  calorimetric  numbers  were 
used.  The  additive  constant  which  thus  remained  un- 
determined for  energy  was  later  finally  fixed  by  the 
^  I  relativistic  law  of  the  proportionality  between  energy  and 
inertia  (15). 

As  in  the  case  of  energy,  it  is  now  possible  to  define 
an  absolute  value  of  entropy,  and  thus  of  physical  prob- 
ability, by  fixing  the  additive  constant  so  that  together 
with  the  energy  (or  better  still,  the  temperature)  the  entropy 
also  should  vanish.  Such  considerations  led  to  a  compara- 
tively simple  method  of  calculating  the  physical  probability 
of  a  given  distribution  of  energy  in  a  system  of  resonators, 
which  yielded  precisely  the  same  expression  for  entropy  as 
that  corresponding  to  the  radiation  law  (16);  and  it  gave  me 
particular  satisfaction,  in  compensation  for  the  many 
disappointments  I  had  encountered,  to  learn  from  Ludwig 
Boltzmann  of  his  interest  and  entire  acquiescence  in  my 
i  new  line  of  reasoning. 

To  work  out  these  probability  considerations  the  know- 
ledge of  two  universal  constants  is  required,  each  of  which 
has  an  independent  meaning,  so  that  the  evaluation  of 
these  constants  from  the  radiation  law  could  serve  as  an 
a  posteriori  test  whether  the  whole  process  is  merely 
a  mathematical  artifice  or  has  a  true  physical  meaning. 
The  first  constant  is  of  a  somewhat  formal  nature ;  it  is 
connected  with  the  definition  of  temperature.  If  tempera- 
ture were  defined  as  the  mean  kinetic  energy  of  a  molecule 


(11) 

in  a  perfect  gas,  which  is  a  minute  energy  indeed,  this 
constant  would  have  the  value  §(17).  But  in  the  con- 
ventional scale  of  temperature  the  constant  assumes 
(instead  of  f )  an  extremely  small  value,  which  naturally  is 
intimately  connected  with  the  energy  of  a  single  molecule, 
so  that  its  accurate  determination  would  lead  to  the 
calculation  of  the  mass  of  a  molecule  and  of  associated 
magnitudes.  This  constant  is  frequently  termed  Boltz- 
mann's  constant,  although  to  the  best  of  my  knowledge 
Boltzmann  himself  never  introduced  it  (an  odd  circum- 
stance, which  no  doubt  can  be  explained  by  the  fact  that 
he,  as  appears  from  certain  of  his  statements  (18),  never 
believed  it  would  be  possible  to  determine  this  constant 
accurately).  Nothing  can  better  illustrate  the  rapid 
progress  of  experimental  physics  within  the  last  twenty 
years  than  the  fact  that  during  this  period  not  only  one, 
but  a  host  of  methods  have  been  discovered  by  means  of 
which  the  mass  of  a  single  molecule  can  be  measured  with 
almost  the  same  accuracy  as  that  of  a  planet. 

While  at  the  time  when  I  carried  out  this  calculation  on  ( 
the  basis  of  the  radiation  law  an  exact  test  of  the  value  thus 
obtained  was  quite  impossible,  and  one  could  scarcely  hope 
to  do  more  than  test  the  admissibility  of  its  order  of 
magnitude,  it  was  not  long  before  E.  Eutherford  and 
H.  Geiger  (19)  succeeded,  by  means  of  a  direct  count  of  the 
a-particles,  in  determining  the  value  of  the  electrical  ele- 
mentary charge  as  4  •  65 . 10~10,  the  agreement  of  which  with 
my  value  4  •  69 . 10~10  could  be  regarded  as  a  decisive  con- 
firmation of  my  theory.  Since  then  further  methods  have 
been  developed  by  E.  Eegener,  R  A.  Millikan,  and  others  (20), 
which  have  led  to  a  but  slightly  higher  value. 

Much  less  simple  than  that  of  the  first  was  the  interpreta- 


(12) 

tion  of  the  second  universal  constant  of  the  radiation  law, 
which,  as  the  product  of  energy  and  time  (amounting  on  a 
first  calculation  to  6  •  55 . 10~27  erg.  sec.)  I  called  the  elemen- 
tary quantum  of  action.  While  this  constant  was  abso- 
lutely indispensable  to  the  attainment  of  a  correct  expression 
for  entropy — for  only  with  its  aid  could  be  determined  the 
magnitude  of  the  '  elementary  region '  or  '  range '  of  prob- 
ability, necessary  for  the  statistical  treatment  of  the 
problem  (21) — it  obstinately  withstood  all  attempts  at  fit- 
ting it,  in  any  suitable  form,  into  the  frame  of  the  classical 
theory.  So  long  as  it  could  be  regarded  as  infinitely  small, 
that  is  to  say  for  large  values  of  energy  or  long  periods  of 
time,  all  went  well;  but  in  the  general  case  a  difficulty 
arose  at  some  point  or  other,  which  became  the  more  pro- 
nounced the  weaker  and  the  more  rapid  the  oscillations. 
The  failure  of  all  attempts  to  bridge  this  gap  soon  placed 
one  before  the  dilemma :  either  the  quantum  of  action  was 
only  a  fictitious  magnitude,  and,  therefore,  the  entire  de- 
duction from  the  radiation  law  Was  illusory  and  a  mere 
juggling  with  formulae,  or  there  is  at  the  bottom  of  this 
method  of  deriving  the  radiation  law  some  true  physical 
concept.  If  the  latter  were  the  case,  the  quantum  would 
have  to  play  a  fundamental  role  in  physics,  heralding  the 
advent  of  a  new  state  of  things,  destined,  perhaps,  to  trans- 
form completely  our  physical  concepts  which  since  the 
introduction  of  the  infinitesimal  calculus  by  Leibniz  and 
Newton  have  been  founded  upon  the  assumption  of  the 
continuity  of  all  causal  chains  of  events. 

Experience  has  decided  for  the  second  alternative.  But 
that  the  decision  should  come  so  soon  and  so  unhesitatingly 
was  due  not  to  the  examination  of  the  law  of  distribution 
of  the  energy  of  heat  radiation,  still  less  to  my  special 


(13) 

deduction  of  this  law,  but  to  the  steady  progress  of  the 
work  of  those  investigators  who  have  applied  the  concept 
of  the  quantum  of  action  to  their  researches. 

The  first  advance  in  this  field  was  made  by  A.  Einstein, 
who  on  the  one  hand  pointed  out  that  the  introduction  of 
the  quanta  of  energy  associated  with  the  quantum  of  action 
seemed  capable  of  explaining  readily  a  series  of  remarkable 
properties  of  light  action  discovered  experimentally,  such 
as  Stokes's  rule,  the  emission  of  electrons,  and  the  ioniza- 
tion  of  gases  (22),  and  on  the  other  hand,  by  the  identification 
of  the  expression  for  the  energy  of  a  system  of  resonators 
with  the  energy  of  a  solid  body,  derived  a  formula  for  the 
specific  heat  of  solid  bodies  which  on  the  whole  represented 
it  correctly  as  a  function  of  temperature,  more  especially 
exhibiting  its  decrease  with  falling  temperature  (23).  A 
number  of  questions  were  thus  thrown  out  in  different 
directions,  of  which  the  accurate  and  many-sided  investiga- 
tions yielded  in  the  course  of  time  much  valuable  material. 
It  is  not  my  task  to-day  to  give  an  even  approximately 
complete  report  of  the  successful  work  achieved  in  this 
field ;  suffice  it  to  give  the  most  important  and  character- 
istic phase  of  the  progress  of  the  new  doctrine. 

First,  as  to  thermal  and  chemical  processes.  With  regard 
to  specific  heat  of  solid  bodies,  Einstein's  view,  which  rests 
on  the  assumption  of  a  single  free  period  of  the  atoms,  was 
extended  by  M.  Born  and  Th.  von  Karman  to  the  case 
which  corresponds  better  to  reality,  viz.  that  of  several  free 
periods  (24) ;  while  P.  Debye,  by  a  bold  simplification  of 
the  assumptions  as  to  the  nature  of  the  free  periods,  suc- 
ceeded in  developing  a  comparatively  simple  formula  for 
the  specific  heat  of  solid  bodies  (25)  which  excellently  repre- 
sents its  values,  especially  those  for  low  temperatures 


(14) 

obtained  by  W.  Nernst  and  his  pupils,  and  which,  moreover, 
is  compatible  with  the  elastic  and  optical  properties  of  such 
bodies.  But  the  influence  of  the  quanta  asserts  itself  also 
in  the  case  of  the  specific  heat  of  gases.  At  the  very 
outset  it  was  pointed  out  by  W.  Nernst(26)  that  to  the 
energy  quantum  of  vibration  must  correspond  an  energy 
quantum  of  rotation,  and  it  was  therefore  to  be  expected 
that  the  rotational  energy  of  gas  molecules  would  also 
vanish  at  low  temperatures.  This  conclusion  was  confirmed 
by  measurements,  due  to  A.  Eucken,  of  the  specific  heat  of 
hydrogen  (27) ;  and  if  the  calculations  of  A.  Einstein  and 
O.  Stern,  P.  Ehrenfest,  and  others  have  not  as  yet  yielded 
completely  satisfactory  agreement,  this  no  doubt  is  due  to 
our  imperfect  knowledge  of  the  structure  of  the  hydrogen 
atom.  That  l quantized'  rotations  of  gas  molecules  (i.e. 
satisfying  the  quantum  condition)  do  actually  occur  in 
nature  can  no  longer  be  doubted,  thanks  to  the  work  on 
absorption  bands  in  the  infra-red  of  N.  Bjerrum,  E.  v.  Bahr, 
H.  Rubens  and  G.  Hettner,  and  others,  although  a  com- 
pletely exhaustive  explanation  of  their  remarkable  rotation 
spectra  is  still  outstanding. 

Since  all  affinity  properties  of  a  substance  are  ultimately 
determined  by  its  entropy,  the  quantic  calculation  of  en- 
tropy also  gives  access  to  all  problems  of  chemical  affinity. 
The  absolute  value  of  the  entropy  of  a  gas  is  characterized 
by  Nernst's  chemical  constant,  which  was  calculated  by 
O.  Sackur  by  a  straightforward  combinatorial  process  simi- 
lar to  that  applied  to  the  case  of  the  oscillators  (28),  while 
H.  Tetrode,  holding  more  closely  to  experimental  data, 
determined,  by  a  consideration  of  the  process  of  vaporiza- 
tion, the  difference  of  entropy  between  a  substance  and  its 
vapour  (29). 


(15) 

While  the  cases  thus  far  considered  have  dealt  with 
states  of  thermodyiiamical  equilibrium,  for  which  the  mea- 
surements could  yield  only  statistical  averages  for  large 
numbers  of  particles  and  for  comparatively  long  periods  of 
time,  the  observation  of  the  collisions  of  electrons  leads 
directly  to  the  dynamic  details  of  the  processes  in  question. 
Therefore  the  determination,  carried  out  by  J.  Franck  and 
G.  Hertz,  of  the  so-called  resonance  potential  or  the  critical 
velocity  which  an  electron  impinging  upon  a  neutral  atom 
must  have  in  order  to  cause  it  to  emit  a  quantum  of  light, 
provides  a  most  direct  method  for  the  measurement  of  the 
quantum  of  action  (30).  Similar  methods  leading  to  per- 
fectly consistent  results  can  also  be  developed  for  the 
excitation  of  the  characteristic  X-ray  radiation  discovered 
by  C.  G.  Barkla,  as  can  be  judged  from  the  experiments 
of  D.  L.  Webster,  E.  Wagner,  and  others. 

The  inverse  of  the  process  of  producing  light  quanta  by 
the  impact  of  electrons  is  the  emission  of  electrons  on 
exposure  to  light-rays,  or  X-rays,  and  here,  too,  the  energy 
quanta  following  from  the  action  quantum  and  the  vibra- 
tion period  play  a  characteristic  role,  as  was  early  recognized 
from  the  striking  fact  that  the  velocity  of  the  emitted 
electrons  depends  not  upon  the  intensity  (31)  but  only  on 
the  colour  of  the  impinging  light  (32).  But  quantitatively 
also  the  relations  to  the  light  quantum,  pointed  out  by 
Einstein  (p.  13),  have  proved  successful  in  every  direction, 
as  was  shown  especially  by  K.  A.  Millikan,  by  measure- 
ments of  the  velocities  of  emission  of  electrons  (33),  while 
the  importance  of  the  light  quantum  in  inducing  photo- 
chemical reactions  was  disclosed  by  E.  Warburg  (34). 

Although  the  results  I  have  hitherto  quoted  from  the  most 
diverse  chapters  of  physics,  taken  in  their  totality,  form  an 


(16) 

overwhelming  proof  of  the  existence  of  the  quantum  of 
action,  the  quantum  hypothesis  received  its  strongest  sup- 
port from  the  theory  of  the  structure  of  atoms  (Quantum 
Theory  of  Spectra)  proposed  and  developed  by  Niels  Bohr. 
For  it  was  the  lot  of  this  theory  to  find  the  long-sought  key 
to  the  gates  of  the  wonderland  of  spectroscopy  which  since 
the  discovery  of  spectrum  analysis  up  to  our  days  had  stub- 
bornly refused  to  yield.  And  the  way  once  clear,  a  stream 
of  new  knowledge  poured  in  a  sudden  flood,  not  only  over 
this  entire  field  but  into  the  adjacent  territories  of  physics 
and  chemistry.  Its  first  brilliant  success  was  the  derivation 
of  Balmer's  formula  for  the  spectrum  series  of  hydrogen  and 
helium,  together  with  the  reduction  of  the  universal  con- 
stant of  Eydberg  to  known  magnitudes  (35) ;  and  even  the 
small  differences  of  the  Eydberg  constant  for  these  two 
gases  appeared  as  a  necessary  consequence  of  the  slight 
wobbling  of  the  massive  atomic  nucleus  (accompanying  the 
motion  of  electrons  around  it).  As  a  sequel  came  the 
investigation  of  other  series  in  the  visual  and  especially 
the  X-ray  spectrum  aided  by  Kitz's  resourceful  combination 
principle,  which  only  now  was  recognized  in  its  funda- 
mental significance. 

But  whoever  may  have  still  felt  inclined,  even  in  the 
face  of  this  almost  overwhelming  agreement — all  the  more 
convincing,  in  view  of  the  extreme  accuracy  of  spectro- 
scopic  measurements — to  believe  it  to  be  a  coincidence, 
must  have  been  compelled  to  give  up  his  last  doubt  when 
A.  Sommerfeld  deduced,  by  a  logical  extension  of  the  laws 
of  the  distribution  of  quanta  in  systems  with  several  degrees 
of  freedom,  and  by  a  consideration  of  the  variability  of 
inert  mass  required  by  the  principle  of  relativity,  that 
magic  formula  before  which  the  spectra  of  both  hydrogen 


(17) 

and  helium  revealed  the  mystery  of  their  '  fine  structure '  (36), 
as  far  as  this  could  be  disclosed  by  the  most  delicate 
measurements  possible  up  to  the  present,  those  of 
F.  Paschen  (37) — a  success  equal  to  the  famous  discovery 
of  the  planet  Neptune,  the  presence  and  orbit  of  which 
were  calculated  by  Leverrier  [and  Adams]  before  man 
ever  set  eyes  upon  it.  Progressing  along  the  same  road, 
P.  Epstein  achieved  a  complete  explanation  of  the  Stark  effect 
of  the  electrical  splitting  of  spectral  lines  (38),  P.  Debye  ob- 
tained a  simple  interpretation  of  the  K-series(39)  of  the  X-ray 
spectrum  investigated  by  Manne  Siegbahn,  and  then  followed 
a  long  series  of  further  researches  which  illuminated  with 
greater  or  less  success  the  dark  secret  of  atomic  structure. 

After  all  these  results,  for  the  complete  exposition  of 
which  many  famous  names  would  here  have  to  be  men- 
tioned, there  must  remain  for  an  observer,  who  does  not 
choose  to  pass  over  the  facts,  no  other  conclusion  than  that 
the  quantum  of  action,  which  in  every  one  of  the  many 
and  most  diverse  processes  has  always  the  same  value, 
namely  6  •  52 . 10~27  erg.  sec.  (40),  deserves  to  be  definitely 
incorporated  into  the  system  of  the  universal  physical  con- 
stants. It  must  certainly  appear  a  strange  coincidence  that 
at  just  the  same  time  as  the  idea  of  general  relativity  arose 
and  scored  its  first  great  successes,  nature  revealed,  pre- 
cisely in  a  place  where  it  was  the  least  to  be  expected,  an 
absolute  and  strictly  unalterable  unit,  by  means  of  which 
the  amount  of  action  contained  in  a  space-time  element  can 
be  expressed  by  a  perfectly  definite  number,  and  thus  is 
deprived  of  its  former  relative  character. 

Of  course  the  mere  introduction  of  the  quantum  of  action 
does  not  yet  mean  that  a  true  Quantum  Theory  has  been 
established.  Nay,  the  path  which  research  has  yet  to  cover 


(18) 

to  reach  that  goal  is  perhaps  not  less  long  than  that  from 
the  discovery  of  the  velocity  of  light  by  Olaf  Romer  to  the 
foundation  of  Maxwell's  theory  of  light.  The  difficulties 
which  the  introduction  of  the  quantum  of  action  into  the 
well-established  classical  theory  has  encountered  from  the 
outset  have  already  been  indicated.  They  have  gradually 
increased  rather  than  diminished ;  and  although  research 
in  its  forward  march  has  in  the  meantime  passed  over 
some  of  them,  the  remaining  gaps  in  the  theory  are  the 
more  distressing  to  the  conscientious  theoretical  physicist. 
In  fact,  what  in  Bohr's  theory  served  as  the  basis  of  the 
laws  of  action  consists  of  certain  hypotheses  which  a  genera- 
tion ago  would  doubtless  have  been  flatly  rejected  by 
every  physicist.  That  with  the  atom  certain  quantized 
orbits  [i.e.  picked  out  on  the  quantum  principle]  should  play 
a  special  role  could  well  be  granted ;  somewhat  less  easy 
to  accept  is  the  further  assumption  that  the  electrons 
moving  on  these  curvilinear  orbits,  and  therefore  accel- 
erated, radiate  no  energy.  But  that  the  sharply  denned 
frequency  of  an  emitted  light  quantum  should  be  different 
from  the  frequency  of  the  emitting  electron  would  be  re- 
garded by  a  theoretician  who  had  grown  up  in  the  classical 
school  as  monstrous  and  almost  inconceivable. 

But  numbers  decide,  and  in  consequence  the  tables  have 
been  turned.  While  originally  it  was  a  question  of  fitting 
in  with  as  little  strain  as  possible  a  new  and  strange  ele- 
ment into  an  existing  system  which  was  generally  regarded 
as  settled,  the  intruder,  after  having  won  an  assured  posi- 
tion, now  has  assumed  the  offensive ;  and  it  now  appears 
certain  that  it  is  about  to  blow  up  the  old  system  at  some 
point.  The  only  question  now  is,  at  what  point  and  to 
what  extent  this  will  happen.  If  I  may  express  at  the 


(19) 

present  time  a  conjecture  as  to  the  probable  outcome  of 
this  desperate  struggle,  everything  appears  to  indicate  that 
out  of  the  classical  theory  the  great  principles  of  thermo- 
dynamics will  not  only  maintain  intact  their  central  position 
in  the  quantum  theory,  but  will  perhaps  even  extend  their 
influence.  The  significant  part  played  in  the  origin  of  the 
classical  thermodynamics  by  mental  experiments  is  now 
taken  over  in  the  quantum  theory  by  P.  Ehrenfest's  hypo- 
thesis of  the  adiabatic  invariance  (41) ;  and  just  as  the 
principle  introduced  by  K.  Clausius,  that  any  two  states  of 
a  material  system  are  mutually  interconvertible  on  suitable 
treatment  by  reversible  processes,  formed  the  basis  for  the 
measurement  of  entropy,  just  so  do  the  new  ideas  of  Bohr 
show  a  way  into  the  midst  of  the  wonderland  he  has 
discovered. 

There  is  one  particular  question  the  answer  to  which 
will,  in  my  opinion,  lead  to  an  extensive  elucidation  of  the 
entire  problem.  What  happens  to  the  energy  of  a  light- 
quantum  after  its  emission  ?  Does  it  pass  outwards  in  all 
directions,  according  to  Huygens's  wave  theory,  continually 
increasing  in  volume  and  tending  towards  infinite  dilution  ? 
Or  does  it,  as  in  Newton's  emanation  theory,  fly  like  a  pro- 
jectile in  one  direction  only?  In  the  former  case  the 
quantum  would  never  again  be  in  a  position  to  concentrate 
its  energy  at  a  spot  strongly  enough  to  detach  an  electron 
from  its  atom  ;  while  in  the  latter  case  it  would  be  neces- 
sary to  sacrifice  the  chief  triumph  of  Maxwell's  theory — the 
continuity  between  the  static  and  the  dynamic  fields — and 
with  it  the  classical  theory  of  the  interference  phenomena 
which  accounted  for  all  their  details,  both  alternatives 
leading  to  consequences  very  disagreeable  to  the  modern 
theoretical  physicist. 


(20) 

Whatever  the  answer  to  this  question,  there  can  be  no 
doubt  that  science  will  some  day  master  the  dilemma,  and 
what  may  now  appear  to  us  unsatisfactory  will  appear  from 
a  higher  standpoint  as  endowed  with  a  particular  harmony 
and  simplicity.  But  until  this  goal  is  reached  the  problem 
of  the  quantum  of  action  will  not  cease  to  stimulate 
research,  and  the  greater  the  difficulties  encountered  in 
its  solution  the  greater  will  be  its  significance  for  the 
broadening  and  deepening  of  all  our  physical  knowledge. 


NOTES 

The  references  to  the  literature  are  not  claimed  to  be  in  any  way 
complete,  and  are  intended  to  serve  only  for  a  preliminary  orientation. 

(1)  G.  Kirchhoff,  Uber  das  Verhaltnis  zwischen  dem  Emissionsver- 
mogen  und  dem  Absorptionsvermogen  der  Korper  fur  Warme   und 
Licht.     Gesammelte  Abhandlungen.     Leipzig,  J.  A.  Barth,  1882,  p.  597 

(§  17). 

(2)  H.  Hertz,  Ann.  d.  Phys.  36,  p.  1,  1889. 

(3)  Sitz.-Ber.  d.  Preuss.  Akad.  d.  Wiss.  Febr.  20,  1896.    Ann.  d.  Phys. 
60,  p.  577,  1897. 

(4)  Sitz.-Ber.  d.  Preuss.  Akad.  d.  Wiss.  May  18,  1899,  p.  455. 

(5)  L.  Boltzmann,  Sitz.-Ber.  d.  Preuss.  Akad.  d.  Wiss.  March  3,  1898, 
p.  182. 

(6)  W.  Wien,  Ann.  d.  Phys.  58,  p.  662,  1896. 

(7)  According   to   Wien's   law   of   the   distribution   of   energy  the 
dependence  of  the  energy  U  of  the  resonator  upon  the  temperature 
is  given  by  a  relation  of  the  form  : 

b 

U=a.e~r. 
Since 

1_  dS 

T~  dlf 

where  S  is  the  entropy  of  the  resonator,  we  have  for  E  as  used  in  the 
text: 


(8)  According  to  Wien's   displacement   law,   the  energy   U  of  the 
resonator  with  the  natural  vibration  period  i/f  is  expressed  by  : 


(9)  Ann.  d.  Phys.  1,  p.  719,  1900. 

(10)  0.  Lurnmer  und  E.  Pringsheim,  Verhandl  der  Deutschen  Physikal. 
Ges.,  2,  p.  163,  1900. 

(11)  H.  Kubens  and  F.  Kurlbaum,  Sitz.-Ber.  der  Preuss.  Akad  d.  Wiss. 
Oct.  25,  1900,  p.  929. 


(22) 

(12)  It  follows  from  the  experiments  of  H.  Rubens  and  F.  Kurlbaum 
that,  for  high  temperatures,  U=cT.      Then,  in  accordance  with  the 
method  quoted  in  (7) : 

_       d*S  U2 

(13)  Put 

then  by  integration, 

--  —  -  -lo    h       - 

whence  the  radiation  formula, 

U=bc:(e-b/T-l). 

Cf.  Verhandlungen  der  Deutschen  Phys.  Ges.  Oct.  19,  1900,  p.  202. 

(14)  Cf.  W.  Nernst  und  Th.  Wulf,  Verh.  d.  Deutsch.  Phys.  Ges.  21, 
p.  294,  1919. 

(15)  For  the  absolute  value  of  the  energy  is  equal  to  the  product 
of  the  inert  mass  and  the  square  of  light  velocity. 

(16)  Verhandlungen  der  Deutschen  Phys.  Ges.  Dec.  14,  1900,  p.  237. 

(17)  Generally,  if  k  be  the  first  radiation  constant,  the  mean  kinetic 
energy  of  a  gas  molecule  is : 

If  we  put,  therefore,  T  =  V,  then  k  =  §.  In  the  conventional  [absolute 
Kelvinian]  temperature  scale,  however,  T  is  defined  by  putting  the 
temperature  difference  between  boiling  and  freezing  water  equal  to  100. 

(18)  Cf.  for  example  L.  Boltzmann,  Zur  Erinnerung  an  Josef  Loschmidt, 
Populdre  Schriften,  p.  245,  1905. 

(19)  E.  Rutherford  and  H.  Geiger,  Proc.  Boy.  Soc.  A.  Vol.  81,  p.  162, 
1908. 

(20)  Cf.  R.  A.  Millikan,  Phys.  Zeitschr.  14,  p.  796,  1913. 

(21)  The  evaluation  of  the  probability  of  a  physical  state  is  based 
upon  counting  that  finite  number  of  equally  probable  special  cases 
by  which  the  corresponding  state  is  realized  ;    and  in  order  sharply 
to  distinguish  these  cases  from  one  another,  a  definite  concept  of  each 
special  case  has  necessarily  to  be  introduced. 

(22)  A.  Einstein,  Ann.  d.  Phys.  17,  p.  132,  1905. 

(23)  A.  Einstein,  Ann.  d.  Phys.  22,  p.  180,  1907. 

(24)  M.  Born  und  Th.  v.  Karman,  Phys.  Zeitschr.  14,  p.  15,  1913. 

(25)  P.  Debye,  Ann.  d.  Phys.  39,  p.  789,  1912. 

(26)  W.  Nernst,  Phys.  Zeitschr.  13,  p.  1064,  1912. 


(23) 

(27)  A.  Euckeri,  Sitz.-Ber.  d.  preuss.  Akad.  d.  Wiss.  p.  141,  1912. 

(28)  0.  Sackur,  Ann.  d.  Phys.  36,  p.  958,  1911. 

029)  H.  Tetrode,  Proc.  Acad.  Sci.  Amsterdam,  Febr.  27  and  March  27, 
1915. 

(30)  J.  Franck  und  G.  Hertz,  Verh.  d.  Deutsch.  Phys.  G-es.  16,  p.  512, 
1914. 

(31)  Ph.  Lenard,  Ann.  d.  Phys.  8,  p.  149,  1902. 

(32)  E.  Ladenburg,  Verh.  d.  Deutschen  Phys.  G-es.  9,  p.  504,  1907. 

(33)  K.  A.  Millikan,  Phys.  Zeitschr.  17,  p.  217,  1916. 

(34)  E.  Warburg,   Uber   den   Energieumsatz   bei   photochemischen 
Vorgangen  in  Gasen.     Sitz.-Ber.  d.  preuss.  Akad.  d.  Wiss.  from  1911 
onwards. 

(35)  N.  Bohr,  Phil  Mag.  30,  p.  394,  1915. 

(36)  A.  Sommerfeld,  Ann.  d.  Phys.  51,  pp.  1,  125,  1916. 

(37)  F.  Paschen,  Ann.  d.  Phys.  50,  p.  901,  1916. 

(38)  P.  Epstein,  Ann.  d.  Phys.  50,  p.  489,  1916. 

(39)  P.  Debye,  Phys.  Zeitschr.  18,  p.  276,  1917. 

(40)  E.  Wagner,  Ann.  d.  Phys.  57,  p.  467,  1918. 

(41)  P.  Ehrenfest,  Ann.  d.  Phys.  51,  p.  327,  1916. 


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