History of atomic

theory

Atomic theory is t he scient ific t heory t hat mat t er is composed of part icles called at oms. The
definit ion of t he word "at om" has changed over t he years in response t o scient ific discoveries.
Init ially, it referred t o a hypot het ical concept of t here being some fundament al part icle of
mat t er, t oo small t o be seen by t he naked eye, t hat could not be divided. Then t he definit ion was
refined t o being t he basic part icles of t he chemical element s, when chemist s observed t hat
element s seemed t o combine wit h each ot her in rat ios of small whole numbers. Then physicist s
discovered t hat t hese part icles had an int ernal st ruct ure of t heir own and t herefore perhaps did
not deserve t o be called "at oms", but renaming at oms would have been impract ical by t hat point .
 The current theoretical model of
the atom involves a dense nucleus
surrounded by a probabilistic
"cloud" of electrons

At omic t heory is one of t he most import ant scient ific development s in hist ory.

Philosophical atomism
The basic idea t hat mat t er is made up of t iny indivisible part icles is an old idea t hat appeared in
many ancient cult ures. The word atom is derived from t he ancient Greek word atomos,[a] which
means "uncut t able". This ancient idea was based in philosophical reasoning rat her t han scient ific
reasoning. Modern at omic t heory is not based on t hese old concept s.[1][2] In t he early 19t h
cent ury, t he scient ist John Dalt on not iced t hat chemical subst ances seemed t o combine wit h
each ot her by discret e and consist ent unit s of weight , and he decided t o use t he word atom t o
refer t o t hese unit s.[3]

Groundwork
Near t he end of t he 18t h cent ury, a number of import ant development s in chemist ry emerged
wit hout referring t o t he not ion of an at omic t heory. The first was Ant oine Lavoisier redefining an
element as a subst ance which scient ist s could not decompose int o simpler subst ances by
experiment at ion. This brought an end t o t he ancient idea of t he element s of mat t er being fire,
eart h, air, and wat er, which had no experiment al support . Lavoisier showed t hat wat er can be
decomposed int o hydrogen and oxygen, which in t urn he could not decompose int o anyt hing
simpler, t hereby proving t hese are element s.[4] Lavoisier also defined t he law of conservat ion of
mass, which st at es t hat in a chemical react ion, mat t er does not appear nor disappear int o t hin air;
t he t ot al mass remains t he same even if t he subst ances involved were t ransformed. Finally,
t here was t he law of definit e proport ions, est ablished by t he French chemist Joseph Proust in
1797, which st at es t hat if a compound is broken down int o it s const it uent chemical element s,
t hen t he masses of t hose const it uent s will always have t he same proport ions by weight ,
regardless of t he quant it y or source of t he original compound.[5]

Dalton's law of multiple

proportions

From A New System of Chemical

Philosophy (John Dalton 1808).
John Dalt on st udied dat a gat hered by himself and by ot her scient ist s. He not iced a pat t ern t hat
lat er came t o be known as t he law of mult iple proport ions: in compounds which cont ain t wo
part icular element s, t he amount of Element A per measure of Element B will differ across t hese
compounds by rat ios of small whole numbers. This suggest ed t hat each element combines wit h
ot her element s in mult iples of a basic quant it y.

In 1804, Dalt on explained his at omic t heory t o his friend and fellow chemist Thomas Thomson,
who published an explanat ion of Dalt on's t heory in his book A System of Chemistry in 1807.
According t o Thomson, Dalt on's idea first occurred t o him when experiment ing wit h "olefiant gas"
(et hylene) and "carburet t ed hydrogen gas" (met hane). Dalt on found t hat "carburet t ed hydrogen
gas" cont ains t wice as much hydrogen per measure of carbon as "olefiant gas", and concluded
t hat a molecule of "olefiant gas" is one carbon at om and one hydrogen at om, and a molecule of
"carburet t ed hydrogen gas" is one carbon at om and t wo hydrogen at oms.[6] In realit y, an et hylene
molecule has t wo carbon at oms and four hydrogen at oms (C2H4), and a met hane molecule has
one carbon at om and four hydrogen at oms (CH4). In t his part icular case, Dalt on was mist aken
about t he formulas of t hese compounds, and it wasn't his only mist ake. But in ot her cases, he
got t heir formulas right . The following examples come from Dalt on's own books A New System of
Chemical Philosophy (in t wo volumes, 1808 and 1817):

Example 1 — tin oxides: Dalt on ident ified t wo t ypes of t in oxide. One is a grey powder t hat
Dalt on referred t o as "t he prot oxide of t in", which is 88.1% t in and 11.9% oxygen. The ot her is a
whit e powder which Dalt on referred t o as "t he deut oxide of t in", which is 78.7% t in and 21.3%
oxygen. Adjust ing t hese figures, in t he grey powder t here is about 13.5 g of oxygen for every
100 g of t in, and in t he whit e powder t here is about 27 g of oxygen for every 100 g of t in. 13.5
and 27 form a rat io of 1:2. These compounds are known t oday t in(II) oxide (SnO) and t in(IV) oxide
(SnO2). In Dalt on's t erminology, a "prot oxide" is a molecule cont aining a single oxygen at om, and a
"deut oxide" molecule has t wo.[7][8] (Tin oxides are act ually cryst als, t hey don't exist in molecular
form.)

Example 2 — iron oxides: Dalt on ident ified t wo oxides of iron. There is one t ype of iron oxide t hat
is a black powder which Dalt on referred t o as "t he prot oxide of iron", which is 78.1% iron and
21.9% oxygen. The ot her iron oxide is a red powder, which Dalt on referred t o as "t he int ermediat e
or red oxide of iron" which is 70.4% iron and 29.6% oxygen. Adjust ing t hese figures, in t he black
powder t here is about 28 g of oxygen for every 100 g of iron, and in t he red powder t here is
about 42 g of oxygen for every 100 g of iron. 28 and 42 form a rat io of 2:3. These compounds are
iron(II) oxide and iron(III) oxide and t heir formulas are Fe 2O2 and Fe 2O3 respect ively (iron(II)
oxide's formula is normally writ t en as FeO, but here it is writ t en as Fe 2O2 t o cont rast it wit h t he
ot her oxide). Dalt on described t he "int ermediat e oxide" as being "2 at oms prot oxide and 1 of
oxygen", which adds up t o t wo at oms of iron and t hree of oxygen. That averages t o one and a
half at oms of oxygen for every iron at om, put t ing it midway bet ween a "prot oxide" and a
"deut oxide".[9][10]

Example 3 — nitrogen oxides: Dalt on was aware of t hree oxides of nit rogen: "nit rous oxide",
"nit rous gas", and "nit ric acid".[11] These compounds are known t oday as nit rous oxide, nit ric oxide,
and nit rogen dioxide respect ively. "Nit rous oxide" is 63.3% nit rogen and 36.7% oxygen, which
means it has 80 g of oxygen for every 140 g of nit rogen. "Nit rous gas" is 44.05% nit rogen and
55.95% oxygen, which means t here are 160 g of oxygen for every 140 g of nit rogen. "Nit ric acid"
is 29.5% nit rogen and 70.5% oxygen, which means it has 320 g of oxygen for every 140 g of
nit rogen. 80 g, 160 g, and 320 g form a rat io of 1:2:4. The formulas for t hese compounds are N2O,
NO, and NO2.[12][13]

Dalt on defined an at om as being t he "ult imat e part icle" of a chemical subst ance, and he used t he
t erm "compound at om" t o refer t o "ult imat e part icles" which cont ain t wo or more element s. This
is inconsist ent wit h t he modern definit ion, wherein an at om is t he basic part icle of a chemical
element and a molecule is an agglomerat ion of at oms. The t erm "compound at om" was confusing
t o some of Dalt on's cont emporaries as t he word "at om" implies indivisibilit y, but he responded
t hat if a carbon dioxide "at om" is divided, it ceases t o be carbon dioxide. The carbon dioxide
"at om" is indivisible in t he sense t hat it cannot be divided int o smaller carbon dioxide
part icles.[3][14]

Dalt on made t he following assumpt ions on how "element ary at oms" combined t o form
"compound at oms" (what we t oday refer t o as molecules). When t wo element s can only form
one compound, he assumed it was one at om of each, which he called a "binary compound". If t wo
element s can form t wo compounds, t he first compound is a binary compound and t he second is
a "t ernary compound" consist ing of one at om of t he first element and t wo of t he second. If t wo
element s can form t hree compounds bet ween t hem, t hen t he t hird compound is a "quat ernary"
compound cont aining one at om of t he first element and t hree of t he second.[15] Dalt on t hought
t hat wat er was a "binary compound", i.e. one hydrogen at om and one oxygen at om. Dalt on did not
know t hat in t heir nat ural gaseous st at e, t he ult imat e part icles of oxygen, nit rogen, and hydrogen
exist in pairs (O2, N2, and H2). Nor was he aware of valencies. These propert ies of at oms were
discovered lat er in t he 19t h cent ury.

Because at oms are t oo small t o be direct ly weighed using t he met hods of t he 19t h cent ury,
Dalt on inst ead expressed t he weight s of t he myriad at oms as mult iples of t he hydrogen at om's
weight , which Dalt on knew was t he light est element . By his measurement s, 7 grams of oxygen
will combine wit h 1 gram of hydrogen t o make 8 grams of wat er wit h not hing left over, and
assuming a wat er molecule t o be one oxygen at om and one hydrogen at om, he concluded t hat
oxygen's at omic weight is 7. In realit y it is 16. Aside from t he crudit y of early 19t h cent ury
measurement t ools, t he main reason for t his error was t hat Dalt on didn't know t hat t he wat er
molecule in fact has t wo hydrogen at oms, not one. Had he known, he would have doubled his
est imat e t o a more accurat e 14. This error was correct ed in 1811 by Amedeo Avogadro.
Avogadro proposed t hat equal volumes of any t wo gases, at equal t emperat ure and pressure,
cont ain equal numbers of molecules (in ot her words, t he mass of a gas's part icles does not
affect t he volume t hat it occupies).[16] Avogadro's hypot hesis, now usually called Avogadro's law,
provided a met hod for deducing t he relat ive weight s of t he molecules of gaseous element s, for
if t he hypot hesis is correct relat ive gas densit ies direct ly indicat e t he relat ive weight s of t he
part icles t hat compose t he gases. This way of t hinking led direct ly t o a second hypot hesis: t he
part icles of cert ain element al gases were pairs of at oms, and when react ing chemically t hese
molecules oft en split in t wo. For inst ance, t he fact t hat t wo lit ers of hydrogen will react wit h
just one lit er of oxygen t o produce t wo lit ers of wat er vapor (at const ant pressure and
t emperat ure) suggest ed t hat a single oxygen molecule split s in t wo in order t o form t wo
molecules of wat er. The formula of wat er is H2O, not HO. Avogadro measured oxygen's at omic
weight t o be 15.074.[17]

Opposition to atomic theory

Dalt on's at omic t heory at t ract ed widespread int erest but not everyone accept ed it at first . The
law of mult iple proport ions was shown t o not be a universal law when it came t o organic
subst ances, whose molecules can be quit e large. For inst ance, in oleic acid t here is 34 g of
hydrogen for every 216 g of carbon, and in met hane t here is 72 g of hydrogen for every 216 g of
carbon. 34 and 72 form a rat io of 17:36, which is not a rat io of small whole numbers. We know
now t hat carbon-based subst ances can have very large molecules, larger t han any t he ot her
element s can form. Oleic acid's formula is C18H34O2 and met hane's is CH4.[18] The law of mult iple
proport ions by it self was not complet e proof, and it wouldn't be unt il t he end of t he 19t h
cent ury t hat at omic t heory was universally accept ed.

One problem was t he lack of uniform nomenclat ure. The word "at om" implied indivisibilit y, but
Dalt on defined an at om as being t he ult imat e part icle of any chemical subst ance, not just t he
element s or even mat t er per se. This meant t hat "compound at oms" such as carbon dioxide
could be divided, as opposed t o "element ary at oms". Dalt on disliked t he word "molecule",
regarding it as "diminut ive".[3][19] Amadeo Avogadro did t he opposit e, he exclusively used t he word
"molecule" in his writ ings, eschewing t he word "at om", inst ead using t he t erm "element ary
molecule".[20] Jöns Jacob Berzelius used t he t erm "organic at oms" t o refer t o part icles
cont aining t hree or more element s, because he t hought t his only exist ed in organic compounds.
Jean-Bapt ist e Dumas used t he t erms "physical at oms" and "chemical at oms"; a "physical at om" is
a part icle t hat cannot be divided by physical forces such as t emperat ure and pressure, and a
"chemical at om" is a part icle t hat cannot be divided by chemical react ions.[21]

The modern definit ions of atom and molecule—an at om being t he basic part icle of an element ,
and a molecule being an agglomerat ion of at oms—were est ablished in t he lat e half of t he 19t h
cent ury. A key event was t he Karlsruhe Congress in Germany in 1860. As t he first int ernat ional
congress of chemist s, it s goal was t o est ablish some st andards in t he communit y. A major
proponent of t he modern dist inct ion bet ween at oms and molecules was St anislao Cannizzaro.

The various quantities of a particular element involved in the constitution of

different molecules are integral multiples of a fundamental quantity that always
manifests itself as an indivisible entity and which must properly be named atom.
 — Stanislao Cannizzaro,
1860[22]
Cannizzaro crit icized past chemist s such as Berzelius for not accept ing t hat t he part icles of
cert ain gaseous element s are act ually pairs of at oms, which led t o mist akes in t heir formulat ion
of cert ain compounds. Berzelius believed t hat hydrogen gas and chlorine gas part icles are
solit ary at oms. But he observed t hat when one lit er of hydrogen react s wit h one lit er of chlorine,
t hey form t wo lit ers of hydrogen chloride inst ead of one. Berzelius decided t hat Avogadro's law
does not apply t o compounds. Cannizzaro preached t hat if scient ist s just accept ed t he
exist ence of single-element molecules, such discrepancies in t heir findings would be easily
resolved. But Berzelius did not even have a word for t hat . Berzelius used t he t erm "element ary
at om" for a gas part icle which cont ained just one element and "compound at om" for part icles
which cont ained t wo or more element s, but t here was not hing t o dist inguish H2 from H since
Berzelius didn't believe in H2. So Cannizzaro called for a redefinit ion so t hat scient ist s could
underst and t hat a hydrogen molecule can split int o t wo atoms in t he course of a chemical
react ion.[23]

A second object ion t o at omic t heory was philosophical. Scient ist s in t he 19t h cent ury had no
way of direct ly observing at oms. They inferred t he exist ence of at oms t hrough indirect
observat ions, such as Dalt on's law of mult iple proport ions. Some scient ist s, not ably t hose who
ascribed t o t he school of posit ivism, argued t hat scient ist s should not at t empt t o deduce t he
deeper realit y of t he universe but only syst emize what pat t erns t hey can direct ly observe. The
ant i-at omist s argued t hat while at oms might be a useful abst ract ion for predict ing how
element s react , t hey do not reflect concret e realit y.

Such scient ist s were somet imes known as "equivalent ist s", because t hey preferred t he t heory of
equivalent weight s, which is a generalizat ion of Proust 's law of definit e proport ions. For example,
1 gram of hydrogen will combine wit h 8 grams of oxygen t o form 9 grams of wat er, t herefore t he
"equivalent weight " of oxygen is 8 grams. This posit ion was event ually quashed by t wo import ant
advancement s t hat happened lat er in t he 19t h cent ury: t he development of t he periodic t able
and t he discovery t hat molecules have an int ernal archit ect ure t hat det ermines t heir
propert ies.[24]

Isomerism
Scient ist s discovered some subst ances have t he exact same chemical cont ent but different
propert ies. For inst ance, in 1827, Friedrich Wöhler discovered t hat silver fulminat e and silver
cyanat e are bot h 107 part s silver, 12 part s carbon, 14 part s nit rogen, and 16 part s oxygen (we
now know t heir formulas as bot h AgCNO). In 1830 Jöns Jacob Berzelius int roduced t he t erm
isomerism t o describe t he phenomenon. In 1860, Louis Past eur hypot hesized t hat t he molecules
of isomers might have t he same set of at oms but in different arrangement s.[25]

In 1874, Jacobus Henricus van 't Hoff proposed t hat t he carbon at om bonds t o ot her at oms in a
t et rahedral arrangement . Working from t his, he explained t he st ruct ures of organic molecules in
such a way t hat he could predict how many isomers a compound could have. Consider, for
example, pent ane (C5H12). In van 't Hoff's way of modelling molecules, t here are t hree possible
configurat ions for pent ane, and scient ist s did go on t o discover t hree and only t hree isomers of
pent ane.[26][27]

n-pentane isopentane neopentane

Jacobus Henricus van 't Hoff's way of modelling molecular structures correctly predicted the three isomers of pentane
(C5H12).
Isomerism was not somet hing t hat could be fully explained by alt ernat ive t heories t o at omic
t heory, such as radical t heory and t he t heory of t ypes.[28][29]

Mendeleev's periodic table

Dmit rii Mendeleev not iced t hat when he arranged t he element s in a row according t o t heir at omic
weight s, t here was a cert ain periodicit y t o t hem.[30]: 117 For inst ance, t he second element , lit hium,
had similar propert ies t o t he nint h element , sodium, and t he sixt eent h element , pot assium — a
period of seven. Likewise, beryllium, magnesium, and calcium were similar and all were seven
places apart from each ot her on Mendeleev's t able. Using t hese pat t erns, Mendeleev predict ed
t he exist ence and propert ies of new element s, which were lat er discovered in nat ure: scandium,
gallium, and germanium.[30]: 118 Moreover, t he periodic t able could predict how many at oms of
ot her element s t hat an at om could bond wit h — e.g., germanium and carbon are in t he same group
on t he t able and t heir at oms bot h combine wit h t wo oxygen at oms each (GeO2 and CO2).
Mendeleev found t hese pat t erns validat ed at omic t heory because it showed t hat t he element s
could be cat egorized by t heir at omic weight . Insert ing a new element int o t he middle of a period
would break t he parallel bet ween t hat period and t he next , and would also violat e Dalt on's law of
mult iple proport ions.[31]
Mendeleev's periodic table from 1871.

In t he modern periodic t able, t he periodicit y of t he element s ment ioned above is eight rat her
t han seven because t he noble gases were not known back when Mendeleev devised his t able.
The rows also now have different lengt hs (2, 8, 18, and 32) t o fit wit h quant um t heory.

Statistical mechanics
In order t o int roduce t he ideal gas law and st at ist ical forms of physics, it was necessary t o
post ulat e t he exist ence of at oms. In 1738, Swiss physicist and mat hemat ician Daniel Bernoulli
post ulat ed t hat t he pressure of gases and heat were bot h caused by t he underlying mot ion of
molecules.

In 1860, James Clerk Maxwell, who was a vocal proponent of at omism, was t he first t o use
st at ist ical mechanics in physics.[32] Ludwig Bolt zmann and Rudolf Clausius expanded his work on
gases and t he laws of t hermodynamics especially t he second law relat ing t o ent ropy. In t he
1870s, Josiah Willard Gibbs ext ended t he laws of ent ropy and t hermodynamics and coined t he
t erm "st at ist ical mechanics."

At t he beginning of t he 20t h cent ury, Albert Einst ein independent ly reinvent ed Gibbs' laws,
because t hey had only been print ed in an obscure American journal.[33] Einst ein lat er comment ed
t hat had he known of Gibbs' work, he would "not have published t hose papers at all, but confined
myself t o t he t reat ment of some few point s [t hat were dist inct ]."[34] All of st at ist ical mechanics
and t he laws of heat , gas, and ent ropy t ook t he exist ence of at oms as a necessary post ulat e.

Brownian motion
In 1827, t he Brit ish bot anist Robert Brown observed t hat dust part icles inside pollen grains
float ing in wat er const ant ly jiggled about for no apparent reason. In 1905, Einst ein t heorized t hat
t his Brownian mot ion was caused by t he wat er molecules cont inuously knocking t he grains about ,
and developed a mat hemat ical model t o describe it . This model was validat ed experiment ally in
1908 by French physicist Jean Perrin, who used Einst ein's equat ions t o measure t he size of
at oms.[35]

Kinet ic diamet ers of various simple molecules

Molecule Perrin's measurements [36] Modern measurements

Helium 1.7 × 10−10 m 2.6 × 10−10 m

Argon 2.7 × 10−10 m 3.4 × 10−10 m

Mercury 2.8 × 10−10 m 3 × 10−10 m

Hydrogen 2 × 10−10 m 2.89 × 10−10 m

Oxygen 2.6 × 10−10 m 3.46 × 10−10 m

Nit rogen 2.7 × 10−10 m 3.64 × 10−10 m

Chlorine 4 × 10−10 m 3.20 × 10−10 m

Discovery of the electron

A 1905 diagram by J. J. Thomson

illustrating his proposed
arrangements of electrons in an atom.

At oms were t hought t o be t he smallest possible division of mat t er unt il 1897 when J. J.
Thomson discovered t he elect ron t hrough his work on cat hode rays.[37]

A Crookes t ube is a sealed glass cont ainer in which t wo elect rodes are separat ed by a vacuum.
When a volt age is applied across t he elect rodes, cat hode rays are generat ed, creat ing a glowing
pat ch where t hey st rike t he glass at t he opposit e end of t he t ube. Through experiment at ion,
Thomson discovered t hat t he rays could be deflect ed by elect ric fields and magnet ic fields. He
concluded t hat t hese rays, rat her t han being a form of light , were composed of very light
negat ively charged part icles. Thomson called t hese "corpuscles", but ot her scient ist s called
t hem elect rons, following an 1894 suggest ion by George Johnst one St oney for naming t he basic
unit of elect rical charge.[38] He measured t he mass of t he elect ron t o be 1,800 t imes smaller
t han t hat of hydrogen, t he smallest at om. Elect rons are so light yet carry so much charge t hat
Thomson concluded t hey must be t he basic part icles of elect rical effect s.[39]

Thomson was t rying t o explain elect ricit y but his t heory ent ailed t hat t he at om is not t he
indivisible ent it y scient ist s t hought it was. A negat ively charged part of t he at om split s off t o
join wit h an adjacent at om in t he act ion of an elect rical current . When elect rons do not flow t heir
negat ive charge must balanced out by some source of posit ive charge wit hin t he at om so as t o
render t he at om elect rically neut ral. Having no clue as t o t he source of t his posit ive charge, he
t ent at ively proposed a uniform sphere of posit ive charge t hroughout which t he elect rons were
dist ribut ed.[40] This became known as t he plum pudding model.[41]

Discovery of the nucleus

T he Geiger–Marsden experiment
Left: Expected results: alpha particles passing through the plum
pudding model of the atom with negligible deflection.
Right: Observed results: a small portion of the particles were
deflected by the concentrated positive charge of the nucleus.

Thomson's plum pudding model was supplant ed in 1909 by one of his former st udent s, Ernest
Rut herford, who discovered t hat most of t he mass and posit ive charge of an at om is
concent rat ed in a very small fract ion of it s volume, which he assumed t o be at t he very cent er.
Ernest Rut herford and his colleagues Hans Geiger and Ernest Marsden came t o have doubt s
about t he Thomson model aft er t hey encount ered difficult ies when t hey t ried t o build an
inst rument t o measure t he charge-t o-mass rat io of alpha part icles (t hese are posit ively-charged
part icles emit t ed by cert ain radioact ive subst ances such as radium). The alpha part icles were
being scat t ered by t he air in t he det ect ion chamber, which made t he measurement s unreliable.
Thomson had encount ered a similar problem in his work on cat hode rays, which he solved by
creat ing a near-perfect vacuum in his inst rument s. Rut herford didn't t hink he'd run int o t his same
problem because alpha part icles are much heavier t han elect rons. According t o Thomson's model
of t he at om, t he posit ive charge in t he at om is not concent rat ed enough t o produce an elect ric
field st rong enough t o deflect an alpha part icle, and t he elect rons are so light weight t hey should
be pushed aside effort lessly by t he much heavier alpha part icles. Yet t here was scat t ering, so
Rut herford and his colleagues decided t o invest igat e t his scat t ering carefully.[42]

Bet ween 1908 and 1913, Rut herford and his colleagues performed a series of experiment s in
which t hey bombarded t hin foils of met al wit h alpha part icles. They spot t ed alpha part icles
being deflect ed by angles great er t han 90°. To explain t his, Rut herford proposed t hat t he
posit ive charge of t he at om is not dist ribut ed t hroughout t he at om's volume as Thomson
believed, but is concent rat ed in a t iny nucleus at t he cent er. Only such an int ense concent rat ion
of charge could produce an elect ric field st rong enough t o deflect t he alpha part icles as
observed, and for t hat t he nucleus would also have t o be well anchored by having most of t he
at om's mass.[42] Rut herford's model is somet imes called t he "planet ary model".[43]

Bohr model
The planet ary model of t he at om had t wo significant short comings. The first is t hat , unlike
planet s orbit ing a sun, elect rons are charged part icles. An accelerat ing elect ric charge is known
t o emit elect romagnet ic waves according t o t he Larmor formula in classical elect romagnet ism.
An orbit ing charge should st eadily lose energy and spiral t oward t he nucleus, colliding wit h it in a
small fract ion of a second. The second problem was t hat t he planet ary model could not explain
t he highly peaked emission and absorpt ion spect ra of at oms t hat were observed.
 The Bohr model of the atom

Quant um t heory revolut ionized physics at t he beginning of t he 20t h cent ury, when Max Planck
and Albert Einst ein post ulat ed t hat light energy is emit t ed or absorbed in discret e amount s
known as quant a (singular, quantum). This led t o a series of quant um at omic models such as t he
quant um model of Art hur Erich Haas in 1910 and t he 1912 John William Nicholson quant um
at omic model t hat quant ized angular moment um as h/2π.[44][45] In 1913, Niels Bohr incorporat ed
t his idea int o his Bohr model of t he at om, in which an elect ron could only orbit t he nucleus in
part icular circular orbit s wit h fixed angular moment um and energy, it s dist ance from t he nucleus
(i.e., t heir radii) being proport ional t o it s energy.[46] Under t his model an elect ron could not spiral
int o t he nucleus because it could not lose energy in a cont inuous manner; inst ead, it could only
make inst ant aneous "quant um leaps" bet ween t he fixed energy levels.[46] When t his occurred,
light was emit t ed or absorbed at a frequency proport ional t o t he change in energy (hence t he
absorpt ion and emission of light in discret e spect ra).[46]

Bohr's model was not perfect . It could only predict t he spect ral lines of hydrogen, not t hose of
mult ielect ron at oms.[47] Worse st ill, it could not even account for all feat ures of t he hydrogen
spect rum: as spect rographic t echnology improved, it was discovered t hat applying a magnet ic
field caused spect ral lines t o mult iply in a way t hat Bohr's model couldn't explain. In 1916, Arnold
Sommerfeld added ellipt ical orbit s t o t he Bohr model t o explain t he ext ra emission lines, but t his
made t he model very difficult t o use, and it st ill couldn't explain more complex at oms.[48][49]

Discovery of isotopes
While experiment ing wit h t he product s of radioact ive decay, in 1913 radiochemist Frederick
Soddy discovered t hat t here appeared t o be more t han one variet y of some element s.[50] The
t erm isot ope was coined by Margaret Todd as a suit able name for t hese variet ies.[51]

That same year, J. J. Thomson conduct ed an experiment in which he channeled a st ream of neon
ions t hrough magnet ic and elect ric fields, st riking a phot ographic plat e at t he ot her end. He
observed t wo glowing pat ches on t he plat e, which suggest ed t wo different deflect ion
t raject ories. Thomson concluded t his was because some of t he neon ions had a different
mass.[52] The nat ure of t his differing mass would lat er be explained by t he discovery of neut rons
in 1932: all at oms of t he same element cont ain t he same number of prot ons, while different
isot opes have different numbers of neut rons.[53]

Discovery of the proton

In an April 1911 paper, Ernest Rut herford est imat ed t hat t he charge of an at omic nucleus is
roughly half t he at om's at omic weight , judging by how various t ypes of met al foil scat t ered alpha
part icles.[54] In June 1911, t he Dut ch physicist Ant onius van den Broek not ed t hat on t he periodic
t able, each successive chemical element differed in at omic weight on average by 2, and he
suggest ed t hat each element has a unique nuclear charge.[55]

The element s on t he periodic t able were generally arranged in order of increasing at omic weight .
However, in a number of places chemist s chose t o swap t he posit ions of cert ain adjacent
element s so t hat t hey appeared in a group wit h ot her element s wit h similar propert ies. For
inst ance, t ellurium is placed before iodine even t hough t ellurium is heavier t han iodine (127.6 vs
126.9) so t hat iodine can be in t he same column as t he ot her halogens. In 1913, Henry Moseley
discovered t hat at oms of each element , when excit ed, emit X-rays at a frequency proport ional
t o t he element 's posit ion on t he adjust ed periodic t able (see Moseley's law), validat ing t he
aforement ioned adjust ment s.

In 1917 Rut herford bombarded nit rogen gas wit h alpha part icles and observed hydrogen nuclei
being emit t ed from t he gas (Rut herford recognized t hese, because he had previously obt ained
t hem bombarding hydrogen wit h alpha part icles, and observing hydrogen nuclei in t he product s).
Rut herford concluded t hat t he hydrogen nuclei emerged from t he nuclei of t he nit rogen at oms
t hemselves (in effect , he had split a nit rogen).[56]

From his own work and t he work of his st udent s Bohr and Henry Moseley, Rut herford knew t hat
t he posit ive charge of any at om could always be equat ed t o t hat of an int eger number of
hydrogen nuclei. This, coupled wit h t he at omic mass of many element s being roughly equivalent
t o an int eger number of hydrogen at oms – t hen assumed t o be t he light est part icles – led him t o
conclude t hat hydrogen nuclei were singular part icles and a basic const it uent of all at omic
nuclei. He named such part icles prot ons. Furt her experiment at ion by Rut herford found t hat t he
nuclear mass of most at oms exceeded t hat of t he prot ons it possessed; he speculat ed t hat
t his surplus mass was composed of previously unknown neut rally charged part icles, which were
t ent at ively dubbed "neut rons".

Discovery of the neutron

In 1928, Walt er Bot he observed t hat beryllium emit t ed a highly penet rat ing, elect rically neut ral
radiat ion when bombarded wit h alpha part icles. It was lat er discovered t hat t his radiat ion could
knock hydrogen at oms out of paraffin wax. Init ially it was t hought t o be high-energy gamma
radiat ion, since gamma radiat ion had a similar effect on elect rons in met als, but James Chadwick
found t hat t he ionizat ion effect was t oo st rong for it t o be due t o elect romagnet ic radiat ion, so
long as energy and moment um were conserved in t he int eract ion. In 1932, Chadwick exposed
various element s, such as hydrogen and nit rogen, t o t he myst erious "beryllium radiat ion", and by
measuring t he energies of t he recoiling charged part icles, he deduced t hat t he radiat ion was
act ually composed of elect rically neut ral part icles which could not be massless like t he gamma
ray, but inst ead were required t o have a mass similar t o t hat of a prot on. Chadwick now claimed
t hese part icles as Rut herford's neut rons.[57] For his discovery of t he neut ron, Chadwick received
t he Nobel Prize in 1935.[58]
Modern quantum mechanical
models

The five filled atomic orbitals of a

neon atom separated and arranged in
order of increasing energy from left to
right, with the last three orbitals being
equal in energy. Each orbital holds up
to two electrons, which most
probably exist in the zones
represented by the colored bubbles.
Each electron is equally present in
both orbital zones, shown here by
color only to highlight the different
wave phase.

In 1924, Louis de Broglie proposed t hat all part icles—part icularly subat omic part icles such as
elect rons—have an associat ed wave. Erwin Schrödinger, fascinat ed by t his idea, developed an
equat ion[59] t hat describes an elect ron as a wave funct ion inst ead of a point . This approach
predict ed many of t he spect ral phenomena t hat Bohr's model failed t o explain, but it was
difficult t o visualize, and faced opposit ion.[60] One of it s crit ics, Max Born, proposed inst ead t hat
Schrödinger's wave funct ion did not describe t he physical ext ent of an elect ron (like a charge
dist ribut ion in classical elect romagnet ism), but rat her gave t he probabilit y t hat an elect ron
would, when measured, be found at a part icular point .[61] This reconciled t he ideas of wave-like
and part icle-like elect rons: t he behavior of an elect ron, or of any ot her subat omic ent it y, has
bot h wave-like and part icle-like aspect s, and whet her one aspect or t he ot her is observed
depend upon t he experiment .[62]
Schrödinger's wave model for hydrogen replaced Bohr's model, wit h it s neat , clearly defined
circular orbit s. The modern model of t he at om describes t he posit ions of elect rons in an at om in
t erms of probabilit ies. An elect ron can pot ent ially be found at any dist ance from t he nucleus,
but , depending on it s energy level and angular moment um, exist s more frequent ly in cert ain
regions around t he nucleus t han ot hers; t his pat t ern is referred t o as it s at omic orbit al. The
orbit als come in a variet y of shapes—sphere, dumbbell, t orus, et c.—wit h t he nucleus in t he
middle.[63] The shapes of at omic orbit als are found by solving t he Schrödinger equat ion.[64]
Analyt ic solut ions of t he Schrödinger equat ion are known for very few relat ively simple model
Hamilt onians including t he hydrogen at om and t he hydrogen molecular ion.[65] Beginning wit h t he
helium at om—which cont ains just t wo elect rons—numerical met hods are used t o solve t he
Schrödinger equat ion.[66]

Qualit at ively t he shape of t he at omic orbit als of mult i-elect ron at oms resemble t he st at es of
t he hydrogen at om. The Pauli principle requires t he dist ribut ion of t hese elect rons wit hin t he
at omic orbit als such t hat no more t han t wo elect rons are assigned t o any one orbit al; t his
requirement profoundly affect s t he at omic propert ies and ult imat ely t he bonding of at oms int o
molecules.[67]: 182

See also

Physics
portal

Spectroscopy
Atom
 History of molecular theory
Timeline of chemical element
discoveries
Introduction to quantum mechanics
Kinetic theory of gases
Atomism
The Physical Principles of the Quantum
Theory

Footnotes

a. a combination of the negative term "a-" and

"τομή," the term for "cut"

1. Pullman, Bernard (1998). The Atom in the

 History of Human Thought (https://books.g
oogle.com/books?id=IQs5hur-BpgC&q=Leu
cippus+Democritus+atom&pg=PA56) .
Oxford, England: Oxford University Press.
pp. 31–33. ISBN 978-0-19-515040-7.
Archived (https://web.archive.org/web/202
10205165029/https://books.google.com/b
ooks?id=IQs5hur-BpgC&q=Leucippus+Dem
ocritus+atom&pg=PA56) from the original
on 5 February 2021. Retrieved 25 October
2020.
2. Melsen (1952). From Atomos to Atom, pp.
18–19
3. Pullman (1998). The Atom in the History of
Human Thought, p. 201
4. Pullman (1998). The Atom in the History of
Human Thought. p. 197
5. "Law of definite proportions | chemistry" (ht
tps://www.britannica.com/science/law-of-d
efinite-proportions) . Encyclopedia
Britannica. Retrieved 2020-09-03.
6. Thomas Thomson (1831). A History of
Chemistry, Volume 2. p. 291
7. Dalton (1817). A New System of Chemical
Philosophy vol. 2, p. 36
8. Melsen (1952). From Atomos to Atom. p.
137
 9. Dalton (1817). A New System of Chemical
Philosophy vol. 2. pp. 28-34: "the
intermediate or red oxide is 2 atoms
protoxide and 1 of oxygen"
10. Millington (1906). John Dalton, p. 113
11. Dalton (1808). A New System of Chemical
Philosophy vol. 1, pp. 316–319
12. Dalton (1808). A New System of Chemical
Philosophy vol. 1. pp. 316–319
13. Holbrow et al. (2010). Modern Introductory
Physics, pp. 65–66
14. Dalton, quoted in Freund (1904). The Study
of Chemical Composition. p. 288: "I have
chosen the word atom to signify these
ultimate particles in preference to particle,
molecule, or any other diminiutive term,
because I conceive it is much more
expressive; it includes in itself the notion of
indivisible, which the other terms do not. It
may, perhaps, be said that I extend the
application of it too far when I speak of
compound atoms; for instance, I call an
ultimate particle of carbonic acid a
compound atom. Now, though this atom
may be divided, yet it ceases to become
carbonic acid, being resolved by such
division into charcoal and oxygen. Hence I
 conceive there is no inconsistency in
speaking of compound atoms and that my
meaning cannot be misunderstood."
15. Dalton (1817). A New System of Chemical
Philosophy vol. 1, pp. 213–214
16. Avogadro, Amedeo (1811). "Essay on a
Manner of Determining the Relative Masses
of the Elementary Molecules of Bodies, and
the Proportions in Which They Enter into
These Compounds" (http://web.lemoyne.ed
u/~giunta/avogadro.html) . Journal de
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17. Avogadro, Amedeo (1811). "Essai d'une
manière de déterminer les masses
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18. Trusted (1999). The Mystery of Matter, p.
73
19. Freund (1904). The Study of Chemical
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20. Pullman (1998). The Atom in the History of
Human Thought, p. 202
21. Jean-Baptiste Dumas (1836). Leçons sur la
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23. Cannizzaro (1858). Sketch of a Course of
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24. Pullman (1998). The Atom in the History of
Human Thought, p. 226: "The first
development is the establishment of the
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marking the successful climax of
concerted efforts to arrange the chemical
properties of elements according to their
atomic weight. The second is the
emergence of structural chemistry, which
ousted what was a simple and primitive
verbal description of the elemental
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of substances and replaced it with a
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architecture."
25. Pullman (1998). The Atom in the History of
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26. Melsen (1952). From Atomos to Atom, pp.
147–148
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of the linking of atoms was established
that a clear light was thrown on this
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predicts, interprets, and limits the number
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[...] The theory of atomicity has successfully
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Bibliography

Andrew G. van Melsen (1960) [First

published 1952]. From Atomos to Atom:
The History of the Concept Atom.
Translated by Henry J. Koren. Dover
Publications. ISBN 0-486-49584-1.
J. P. Millington (1906). John Dalton (http
s://archive.org/details/in.ernet.dli.2015.
30924/) . J. M. Dent & Co. (London); E.
P. Dutton & Co. (New York).
Jaume Navarro (2012). A History of the
Electron: J. J. and G. P. Thomson.
Cambridge University Press. ISBN 978-1-
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Jennifer Trusted (1999). The Mystery of
Matter. MacMillan. ISBN 0-333-76002-6.
Bernard Pullman (1998). The Atom in the
History of Human Thought. Translated by
Axel Reisinger. Oxford University Press.
ISBN 0-19-511447-7.
Jean Perrin (1910) [1909]. Brownian
Movement and Molecular Reality (https://
archive.org/details/brownianmovement
00perr) . Translated by F. Soddy. Taylor
and Francis.
Ida Freund (1904). The Study of
Chemical Composition. Cambridge
University Press.
Thomas Thomson (1807). A System of
Chemistry: In Five Volumes, Volume 3.
John Brown.
Thomas Thomson (1831). The History of
Chemistry, Volume 2. H. Colburn, and R.
Bentley.
 John Dalton (1808). A New System of
Chemical Philosophy vol. 1 (https://librar
y.si.edu/digital-library/book/new-system
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John Dalton (1817). A New System of
Chemical Philosophy vol. 2 (https://librar
y.si.edu/digital-library/book/new-system
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Stanislao Cannizzaro (1858). Sketch of a
Course of Chemical Philosophy (https://a
rchive.org/details/sketchofcourseof00c
annrich/page/4/mode/2up?q=Berzeliu
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Further reading
Further reading

Charles Adolphe Wurtz (1881) The

Atomic Theory, D. Appleton and
Company, New York.
Alan J. Rocke (1984) Chemical Atomism
in the Nineteenth Century: From Dalton to
Cannizzaro, Ohio State University Press,
Columbus (open access full text at
http://digital.case.edu/islandora/object/
ksl%3Ax633gj985 ).

External links

Wikiquote has quotations related to

Atomic theory.
Atomism (http://faculty.washington.edu/
smcohen/320/atomism.htm) by S.
Mark Cohen.
Atomic Theory (http://www.robotplatfor
m.com/knowledge/Atomic%20Theory/a
tomic_theory.html) – detailed
information on atomic theory with
respect to electrons and electricity.
The Feynman Lectures on Physics Vol. I
Ch. 1: Atoms in Motion (https://www.fey
nmanlectures.caltech.edu/I_01.html)
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