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Hydrogenbondinginwater

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HydrogenBondinginWater
Ahydrogenbondisanattractionbetweenapairofelectronegativeatomsinvolvingahydrogenatomlocated
betweenthem.Hydrogenbondsareresponsibleforthelifegivingpropertiesofwater.

Hydrogenbonds
Waterhydrogenbonds
Hydrogenbondcooperativity
Hydrogenbondsandsolubility
Rearranginghydrogenbonds
Bifurcatedhydrogenbonds
Informationtransfer

Hydrogenbonds
Hydrogenbondingoccurswhenanatomofhydrogenisattractedbyratherstrongforcestotwoatomsinsteadofonly
one,sothatitmaybeconsideredtobeactingasabondbetweenthem[99].h Typicallyhydrogenbondingoccurswhere
thepartiallypositivelychargedhydrogenatomliesbetweenpartiallynegativelychargedoxygenand/ornitrogenatoms,
butisalsofoundelsewhere,suchasbetweenfluorineatomsinHF2(averystronghydrogenbondat163kJmol1)and

betweenwaterandthesmallerhalideionsF,ClandBr(forexample,HOHBr,[178,1190]thestrengthofhydrogen
bondingreducingasthehalideradiusincreases),andtoamuchsmallerextenttoI[190]andevenxenon[941],(avery
weakhydrogenbondat2kJmol1).EvenveryweakCHOH2hydrogenbonds(~4kJmol1)arebeingincreasingly
recognized[1293].Intheoreticalstudies,stronghydrogenbondsevenoccurtothehydrogenatomsinmetalhydrides
(forexample,LiHHF[217]).Thecurrentviewofthehydrogenbondhasbeenreviewed[1462]andcomparisonto
halogenbonds(i.e.CXZX=Cl,Br,IZ=O,N,S),CHinteractions,andCBrinteractionsmade[2248].
Hydrogenbondstrengthisgivenbytheweakerofthetwointeractionsoftheflankingatomswiththecentralhydrogen
atomandisstrongestwhentheseinteractionsareequal[1653].Hydrogenbondstrengthmaybeestimatedtheoretically
fromthequantumtheoryofatomsinmolecules[2191].Hydrogenbondingischaracterizedbyitspreferreddimensions,
molecularorientation,approximatelinearityandchangesininfraredfrequencyandintensity.[BacktoTop ]

Waterhydrogenbonds
Liquidwaterisexceptionalinhavingapproximatelyasmany
hydrogenbondsasithascovalentbonds.Shownrightisthe
numberofhydrogenbondsperwatermoleculeasthetemperature
riseswiththelinewidthshowingtheapproximatedisparitybetween
differentexperimentalmethods(datafrom[2264]).Althoughthere
arereportsofwaterhavingmorethanfourhydrogenbonds(for
example5or6)thesehydrogenbondscannotbespatially
accommodatedaroundthecentralwatermoleculewithoutbeing
sitedfurtherfromthecentraloxygen(seebelow)pluswithoneor
moreoftheoriginalhydrogenbondsbeingsubstantiallyweakened.

Thus,theycanbebifurcatedbondswherethebondisessentially
sharedbetweenthewatermolecules(forexample,twohalfbonds
ratherthanonefullbond).Nostablewaterclusterhasbeenfound
withthecentralwatermolecule5coordinatedbyhydrogenbondingtofivewatermolecules.

Inwater'shydrogenbonds,thehydrogenatomiscovalentlyattachedtotheoxygenofawatermolecule(492.2148kJ
mol1[350])buthas(optimally)anadditionalattraction(about23.3kJmol1a1[168]almost5xtheaveragethermal
collisionfluctuationat25C)a2toaneighboringoxygenatomofanotherwatermoleculethatisfargreaterthanany
includedvanderWaalsinteraction.iHydrogenbondswithinheavywaterarestronger.a3Water'shydrogenbondingholds
watermoleculesuptoabout15%closerthanifthanifwaterwasasimpleliquidwithjustvanderWaalsdispersion
interactions.However,ashydrogenbondingisdirectionalitrestrictsthenumberofneighboringwatermoleculestoabout
fourratherthanthelargernumberfoundinsimpleliquids(forexample,xenonatomshavetwelvenearestneighborsin
theliquidstate.Formationofhydrogenbondsbetweenwatermoleculesgivesrisetolarge,butmostlycompensating,
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energeticchangesinenthalpy(becomingmorenegative)andentropy(becoming
lesspositive).Bothchangesareparticularlylarge,basedbypermassorper
volumebasis,duetothesmallsizeofthewatermolecule.Thisenthalpyentropy
compensationisalmostcomplete,however,withtheconsequencethatverysmall
imposedenthalpicorentropiceffectsmayexertaconsiderableinfluenceon
aqueoussystems.ItispossiblethathydrogenbondsbetweenparaH2O,
possessingnogroundstatespin,arestrongerandlastlongerthanhydrogen
bondsbetweenorthoH2O[1150].

Thehydrogenbondinwaterispart(about90%)electrostaticandpart(about
10%)electronsharing,thatiscovalent[96]d,andmaybeapproximatedby
bondsmadeupofcovalentHOH+OH2,ionicHOH+OH2,andlong
bondedcovalentHOHO+H2partswithHOH+OH2beingverymuch

moreinevidencethanHOHO+H2,wheretherewouldbeexpectedtobe
muchextranonbondedrepulsion.Themovementofelectronsfromtheoxygen
atomtotheOHantibondingorbitalonaneighboringmolecule(HOH+OH2)bothweakenthecovalentOHbond
(solengtheningit)andreducestheHOHOH2'hydrogen'bond.Hydrogenbondingaffectsallthemolecularorbitals

evenincludingtheinnerO1s(1a1)orbitalwhichisbound318kJmol1(3.3eV)lessstronglyinatetrahedrallyhydrogen
bondedbulkliquidphasecomparedtothegasphase[1227].

Clusterslinkedbyextensivehydrogenbondingcanbe
consideredasbeingconnectedbyextensive,but
complementary,electrondelocalization.Longrange
organization(>100nm)hasbeendetectedbyhyper
Rayleighlightscattering(HRS)[2268].Aselectronsare
notheldbyindividualmoleculesbutareeasily
distributedamongstwaterclusterstheycangiveriseto
coherentregions[1691],withcorrelatedmanybody
quantummechanicaltunneling[2297],interactingwith
localelectromagneticradiation.Thewaterprotonsare
alsonotheldbyindividualmoleculesbutmayswitch
partnersinanorderedmannerwithindistinctnetworks
[1504,1699],similartothatoccurringinhexagonalice
[2301].

Directvisualizationofsuchconcertedtunnelinghas
beenachievedbythecleveruseofacryogenicscanning
tunnelingmicroscope[2287].Overshorthydrogen
bondedwaterwires(seeright)therecanbecorrelated
movementofprotonsandelectronsduetoquantum
fluctuations[2025]reinforcingtheconceptofwater
notbeingamolecularliquid.

Thereareeffectivelynofreewatermolecules(i.e.moleculeswithnohydrogenbonds)inliquidwateratambientpressure.

Xrayspectroscopicprobingindicatesthattheelectrontransitionsbetweenmolecularorbitals(changingwiththelocal
hydrogenbondingtopology)withdifferingsuchcontributionsmayshiftonatimescaleoflessthanafemtosecond.
Contributingtothestrengthanddynamics[1673]ofwater'shydrogenbondingarenuclearquantumeffects(zeropoint
vibrationalenergy)whichbiasthelengthoftheOHcovalentbondlongerthanits'equilibrium'positionlength(asthe
shorterHOHOH2hydrogenbondsarestronger),soalsoincreasingtheaveragedipolemoment[554].Nuclear
quantumeffectsgiverisetohighprotonswappingbetweenneighboringwatermoleculesplusstrengtheningofhydrogen
bondsatlowtemperaturesandtheirweakeningathightemperatures[2286].Onformingthehydrogenbond,thedonor
hydrogenatomstretchesawayfromitsoxygenatomandtheacceptorlonepairstretchesawayfromitsoxygenatomand
towardsthedonorhydrogenatom[585],bothoxygenatomsbeingpulledtowardseachother.Thestrongerthe
hydrogenbond,thelongerlivedandthelesseasydoestheprotonescapethetwowatermoleculesinvolved.

Animportantfeatureofthehydrogenbondisthatitpossessesdirectionbyconventionthisdirectionisthatoftheshorter
OH(
)covalentbond(theOHhydrogenatombeingdonatedtotheOatomacceptoratomonanotherH2O
molecule).In1HNMRstudies,thechemicalshiftoftheprotoninvolvedinthehydrogenbondmovesabout0.01ppmK1
upfieldtolowerfrequency(plusabout5.5ppmfurtherupfieldtovaporat100C)thatis,becomesmoreshieldedwith
reducingstrengthofhydrogenbonding[222,1935]asthetemperatureisraisedasimilareffectmaybeseeninwater's
17ONMR,movingabout0.05ppmK1upfieldplus3638ppmfurtherupfieldtovaporat100C.bIncreasedextentof
hydrogenbondingwithinclustersresultsinasimilareffectthatis,higherNMRchemicalshiftswithgreatercooperativity
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[436],shorterhydrogenbondedOHOdistances[1616],smalleratomicvolumeofthehydrogenatom,greaterpositive
chargeonthehydrogenatomsandgreaternegativechargeontheoxygenatoms.Thebondstrengthdependsonits
lengthandangle,withthestrongesthydrogenbondinginwaterexistingintheshortlinearprotoncenteredH5O2+ionat
about120kJmol1.However,smalldeviationsfromlinearityinthebondangle(upto20)possiblyhavearelativelyminor
effect[100].Thedependencyonbondlengthisveryimportantandhasbeenshowntoexponentiallydecaywithdistance
[101].Someresearchersconsiderthehydrogenbondtobebrokencifthebondlengthisgreaterthan3.10orthebond
anglelessthan146[173],c2althoughabinitiocalculationsindicatethatmostofthebondingenergystillremainsand
morebentbutshorterbondsmayberelativelystrongforexample,oneofthehydrogenbondsinicefour(143).
SimilarlyOHOinteractionenergiesbelow10kJmol1havebeentakenasindicativeofbrokenhydrogenbonds
althoughtheyarealmost50%asstrongas'perfect'hydrogenbondsandthereisnoreasontopresupposethatitissolely
thehydrogenbondthathasbeenaffectedwithnocontributionsfromotherinteractions.Also,thestrengthofbonding
mustdependontheorientationandpositionsoftheotherbondedandnonbondedatomsand'lonepair'electrons[525].

Thereisatradeoffbetweenthecovalentandhydrogen
bondstrengthsthestrongeristheHObond,the
weakertheOHcovalentbond,andtheshorterthe
OOdistance[1928](seeright).Interestingly,this
meansthattheOHcovalentpartofthehydrogen
bondsgetsshorterasthetemperatureofthewater
increases.TheweakeningoftheOHcovalentbond
givesrisetoagoodindicatorofhydrogenbonding
energythefractionalincreaseinitslengthdetermined
bytheincreasingstrengthofthehydrogenbonding
[217]forexample,whenthepressureissubstantially
increased(~GPa)theremaininghydrogenbonds
(HO)areforcedshorter[655]causingtheOH
covalentbondstobeelongated.Hydrogenbond
strengthcanbeaffectedbyelectromagneticand
magneticeffects.Dissociationisarareevent,occurring
onlytwiceadaythatis,onlyonceforevery1016times
thehydrogenbondbreaks.

Theanomalouspropertiesofliquidwatermaybe
explainedprimarilyonthebasisofitshydrogen
bonding[1530].[BacktoTop ]

Hydrogenbondcooperativity
Whenahydrogenbondformsbetweentwowatermolecules,theredistributionofelectronschangestheabilityforfurther
hydrogenbonding.Thewatermoleculedonatingthehydrogenatomhasincreasedelectrondensityinits'lonepair'region
[577],whichencourageshydrogenbondacceptance,andtheacceptingwatermoleculehasreducedelectrondensity
centeredonitshydrogenatomsanditsremaining'lonepair'region[577],whichencouragesfurtherdonationbut
discouragesfurtheracceptanceofhydrogenbonds.Thiselectronredistributionthusresultsinboththecooperativity(e.g.
acceptingonehydrogenbondencouragesthedonationofanother)andanticooperativity(forexample,acceptingone
hydrogenbonddiscouragesacceptanceofanother)inhydrogenbondformationinwaternetworks.Cooperativehydrogen
bondingincreasestheOHbondlengthwhilstcausinga20foldgreaterreductionintheHOandOOdistances
[436].TheincreaseinbondlengthhasbeencorrelatedwiththehydrogenbondstrengthandresultantOHstretch
vibrations[1318].ThusOOdistanceswithinclustersarelikelytobeshorterthanthoseattheperiphery,inagreement
withtheicosahedralclustermodel.Ifthehydrogenbondissubstantiallybentthenitfollowsthatthebondstrengthis
weaker.Themaincriteriatodeterminethestrengthofhydrogenbondsaretheir(relativelyinaccuratelydetermined)
intermoleculardistancesandthe(moreprecise)wavenumbersoftheirstretchingvibrationalmodesandthoseofthedonor
hydrogencovalentbond.eAnyfactors,suchaspolarization,thatreducesthehydrogenbondlength,isexpectedto
increaseitscovalency.Thereisstillsomedisputeoverthesizeofthiscovalency,dhoweveranycovalencywillincreasethe
networkstabilityrelativetopurelyelectrostaticeffects.Thehydrogenbondinwaterdimersissufficientlystrongtoresultin
thedimerspersistingwithinthegasstateatsignificantconcentrations[1977](forexample,~0.1%H2Oat25Cand85%
humidity)tocontributesignificantlytotheabsorptionofsunlightandatmosphericreactionkinetics[266].Themolecular
orbitalsinvolvedinthehydrogenbondingbetweentwowatermoleculesandfivewatermoleculesinacyclicpentamerare
givenonotherpages.

Althoughthehydrogenatomsareoftenshownalonglinesconnectingtheoxygenatoms,thisisnowthoughttobe
indicativeoftimeaveragedpositiononlyandunlikelytobefoundtoasignificantextenteveninice.

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Liquidwaterconsistsofamixtureofshort,straightandstrong
hydrogenbondsandlong,weakandbenthydrogenbondswith
manyintermediatebetweentheseextremes.Shorthydrogenbonds
inwaterarestronglycorrelatedwiththembeingstraighter[1083].
Protonmagneticshieldingstudiesgivethefollowingaverage
parametersfortheinstantaneousstructureofliquidwaterat4C
nonlinearity,distancesandvarianceallincreasingwithtemperature
[458].

Notethatthetwowatermoleculesbelowarenotrestrictedto
perpendicularplanesandonlyasmallproportionofhydrogenbonds
arelikelytohavethisaveragedstructure.

Thehydrogenbondlengthofwatervarieswithtemperatureand
pressure.Asthecovalentbondlengthsvarymuchlesswith
temperatureandpressure,mostofthedensificationoficeIhdueto
reducedtemperatureorincreasedpressuremustbeduetoreductionin
thehydrogenbondlength.Thishydrogenbondlengthvariationcanbe
shownfromthechangesinvolumeoficeIh[818].Ashydrogenbond
strengthdependsalmostlinearlyonitslength(shorterlengthgiving
strongerhydrogenbonding),italsodependsalmostlinearly(outside
extremevalues)onthetemperatureandpressure[818].

Thelatestmolecularparametersforwateraregivenelsewhere.TheOOdistanceiniceIhvariesbetween2.75(0K)
and2.764(253K).Theenergyofalinearhydrogenbonddependsontheorientationofthewatermoleculesrelativeto
thehydrogenbond.j

Notethatinliquidwater,thehydrogenbondedarrangementofmostmoleculesisnotassymmetricalasshownhere.In
particular,thepositioningofthewatermoleculesdonatinghydrogenbondstotheacceptingpositionsonawater
molecule(thatis,thewatermoleculesbehindinthediagramabove,labeled'd')arelikelytobelesstetrahedrallyplaced,l
duetothelackofsubstantialtetrahedrallypositioned'lonepair'electrons,thanthosewatermoleculesthatarebeing
donatedtofromthatwatermolecule(thatis,thewatermoleculestopandfrontinthediagramabove,labeled'a'[1224].
Also,thearrangementmaywellconsistofonepairofmoretetrahedrallyarrangedstronghydrogenbonds(onedonorand
oneacceptor)withtheremaininghydrogenbondpair(onedonorandoneacceptor)beingeitherabout6kJmol1weaker
[573],lesstetrahedrallyarranged[373,396]orbifurcated[573]perhapsmainlyduetotheanticooperativityeffects
mentionedbelow.Suchadivisionofwaterintohigher(4linked)andlower(2linked)hydrogenbondcoordinatedwater
hasbeenshownbymodeling[1349].Xrayabsorptionspectroscopyconfirmsthat,atroomtemperature,80%ofthe
moleculesofliquidwaterhaveone(cooperativelystrengthened)stronghydrogenbondedOHgroupandonenon,or
onlyweakly,bondedOHgroupatanyinstant(subfemtosecondaveragedandsuchasmayoccurinpentagonally
hydrogenbondedclusters),theremaining20%ofthemoleculesbeingmadeupoffourhydrogenbondedtetrahedrally
coordinatedclusters[613].Thereismuchdebateastowhethersuchstructuringrepresentsthemoretimeaveraged
structure,whichisunderstoodbysometobebasicallytetrahedral[1024].gEveniftheinstantaneoushydrogenbonded
arrangementistetrahedral,distortionstotheelectrondensitydistributionmaycausethehydrogenbondstohave
differentstrengths[1979,2095].

Liquidwatercontainsbyfarthedensesthydrogenbondingofanysolventwithalmostasmanyhydrogenbondsasthere
arecovalentbonds.Thesehydrogenbondscanrapidlyrearrangeinresponsetochangingconditionsandenvironments
(forexample,solutes).Thehydrogenbondingpatternsarerandominwater(andiceIh)foranywatermoleculechosenat
random,thereisequalprobability(50%)thatthefourhydrogenbonds(thatis,thetwohydrogendonorsandthetwo
hydrogenacceptors)arelocatedatanyofthefoursitesaroundtheoxygen.Watermoleculessurroundedbyfour
hydrogenbondstendtoclumptogether,formingclusters,forbothstatistical[11]andenergeticreasons.Hydrogen
bondedchains(thatis,OHOHO)arecooperative[379]thebreakageofthefirstbondisthehardest,thenthe
nextoneisweakened,andsoon(seethecyclicwaterpentamer).Thusunzippingmayoccurwithcomplexmacromolecules
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heldtogetherbyhydrogenbonding,forexample,nucleicacids.Suchcooperativityisafundamentalpropertyofliquid
waterwherehydrogenbondsareupto250%strongerthanthesinglehydrogenbondinthedimer[77].Astrongbaseat
theendofachainmaystrengthenthebondingfurther.Thecooperativenatureofthehydrogenbondmeansthatacting
asanacceptorstrengthensthewatermoleculeactingasadonor[76].However,thereisananticooperativeaspectinso
farasactingasadonorweakensthecapabilitytoactasanotherdonor,forexample,OHOHO[77].Itisclear
thereforethatawatermoleculewithtwohydrogenbondswhereitactsasbothdonorandacceptorissomewhatstabilized
relativetoonewhereitiseitherthedonororacceptoroftwo.Thisisthereasonwhyitissuspectedthatthefirsttwo
hydrogenbonds(donorandacceptor)giverisetothestrongesthydrogenbonds[79].Aninterestingwayofdescribing
thecooperative/anticooperativenatureofthewaterdimerhydrogenbondistousethenomenclatured'a'DAd''a''where
DArepresentsthedonoracceptornatureofthehydrogenbond,thed'a'representstheremainingdonoracceptorstatus
ofthedonatingwatermoleculeandd''a''representstheremainingdonoracceptorstatusoftheacceptingwatermolecule
[852].Individually,themostenergeticallyfavoreddonatingwatermoleculeshavethestructures02DAxx,12DAxx,01DAxx
and11DAxxwith00DAxxand10DAxxdisfavoredwhereasthemostenergeticallyfavoredacceptingwatermoleculeshave
thestructuresxxDA20,xxDA21,xxDA10andxxDA11withxxDA00andxxDA01disfavored.

Waterhydrogenbonding
anticooperative
cooperative(=d'+a'+d''a'')
2

1
0
1
2
3
increasinghydrogenbondstrength

0k

36

12

18

10DA01 10DA00 10DA10 10DA20

24

30

10DA11 10DA21
00DA01 00DA00 00DA10 00DA20

00DA11 00DA21
11DA01 11DA00 11DA10 11DA20

11DA11 11DA21
01DA01 01DA00 01DA10 01DA20

01DA11 01DA21

12DA01 12DA00 12DA10 12DA20

12DA11 12DA21
02DA01 02DA00 02DA10 02DA20

02DA11 02DA21

Usingquantumchemicalcalculationofdifferentclusters
ofwatermoleculeshasshownthatthehydrogen
bondingstrengthcanvaryforasmuchas90%
betweenextremecasesofcooperativityandanti
cooperativitywithcooperativityincreasing(~3kJmol
1)thebondstrengthandreducing(~0.03)the
hydrogenbondlengthperaddedmoleculeandanti
cooperativityreversingtheseeffectsbythesame
amounts.Thehydrogenbondstrengthiscomputedto
varyforasmuchas90%betweenextremecasesof
cooperativityandanticooperativity[1829].Fromthis
calculation,thedifferenceineffectbetweenthe2
anticooperativeand4cooperativeinteractionsinthe
abovetablewouldbe~18kJmol1and~0.18.

CationsmayinducestrongcooperativehydrogenbondingaroundthemduetothepolarizationofwaterOHbycation
lonepairinteractions(Cation+OHOH).Lucketal[78]introducedacooperativityfactorforthiseffect,whichvaried
astheHofmeisterseriesfromK+(1.08)toZn2+(2.5).Totalhydrogenbondingaroundionsmaybedisruptedhoweveras
iftheelectronpairacceptanceincreases(forexample,inwateraroundcations)sotheelectronpairdonatingpowerof
thesewatermoleculesisreducedwithoppositeeffectsinthehydrationwateraroundanions.Thesechangesinthe
relativehydrationabilityofsaltsolutionsareresponsiblefortheswellinganddeswellingbehaviorofhydrophilicpolymer
gels[317].

Thesubstantialcooperativestrengtheningofhydrogenbondinwaterisdependentonlongrangeinteractions[98].This
cooperativeeffectmaybestrongerinchainsoforthowatermoleculesduetospincoupling[2041].Breakingonebond
generallyweakensfthosearoundwhereasmakingonebondgenerallystrengthensthosearoundandthis,therefore,
encourageslargerclusters,forthesameaveragebonddensity.Thehydrogenbondedclustersizeinwaterat0Chas
beenestimatedtobe400[77,1791].Weaklyhydrogenbondingsurfacerestrictsthehydrogenbondingpotentialof
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adjacentwatersothatthesemakefewerandweakerhydrogenbonds.Ashydrogenbondsstrengtheneachotherina
cooperativemanner,suchweakbondingalsopersistsoverseverallayersandmaycauselocallychangedsolvation.
Conversely,stronghydrogenbondingwillbeevidentatdistance.Theweakeningofhydrogenbonds,fromabout23kJ
mol1toabout17kJmol1,isobservedwhenmanybondsarebrokenatsuperheatingtemperatures(>100C)so
reducingthecooperativity[173].Thebreakageofthesebondsisnotonlyduetothemoreenergeticconditionsathigh
temperaturebutalsoresultsfromarelatedreductioninthehydrogenbonddonatingabilitybyabout10%foreach100
Cincrease[218].Thelossofthesehydrogenbondsresultsinasmallincreaseinthehydrogenbondacceptingabilityof
water,duepossiblytoincreasedaccessibility[218].

Everyhydrogenbondformedincreasesthehydrogenbondstatusoftwowatermoleculesandeveryhydrogenbond
brokenreducesthehydrogenbondstatusoftwowatermolecules.Thenetworkisessentiallycompleteatambient
temperaturesthatis,(almost)allmoleculesarelinkedbyatleastoneunbrokenhydrogenbondedpathway.Hydrogen
bondlifetimesare120ps[255]whereasbrokenbondlifetimesareabout0.1pswiththeproportionof'dangling'
hydrogenbondspersistingforlongerthanapicosecondbeinginsignificant[849].Brokenbondsarebasicallyunstable
[849]andwillprobablyreformtogivesamehydrogenbond(asshownbythesloworthowater/parawaterequilibrium
process[410]),particularlyiftheotherthreehydrogenbondsareinplacehydrogenbondbreakagebeingmore
dependentonthelocalstructuringratherthantheinstantaneoushydrogenbondstrength[833].Ifnot,breakageusually
leadstorotationaroundoneoftheremaininghydrogenbond(s)[673]andnottotranslationaway,astheresultant'free'
hydroxylgroupand'lonepair'arebothquitereactive.Alsoimportant,ifseldomrecognized,isthepossibilityofthe
hydrogenbondbreaking,asevidencedbyphysicaltechniquessuchasIR,RamanorNMRandcausedbylossofhydrogen
bond'covalency'duetoelectronrearrangement,withoutanyangularchangeintheOHOatomicpositions.Thus,
clustersmaypersistformuchlongertimes[329]thancommoninterpretationofdatafromthesemethodsindicates.
EvidenceforthismaybedrawnfromthehighdegreeofhydrogenbondbreakageseenintheIRspectrumofice[699],
wheretheclusteringistakenaslastingessentiallyforever.[BacktoTop ]

Hydrogenbondsandsolubility
Asisclearfromtheoriginofthewordsused,waterisa
goodsolventforhydrophilicsolutes(suchasalcohols)
butapoorsolventforhydrophobicsolutes(suchasthe
noblegases).Thesolubilitieschangesignificantlywith
temperatureandthesechangeshavebeencorrelated
withthehydrogenbondingdonation(acidity)and
acceptance(basicity)changesinthewater.Boththese
factorsreducewithincreasingtemperaturebutto
differentextents[1830].At300Cthesolvent
propertiesofwatertohydrophilicsolutesaresimilarto
thoseofnitrobenzeneoracetonitrileat25Cbut
hydrophobicsolutesremainpoorlysoluble[1830].

Rearranginghydrogenbonds
Water'shydrogenbondsonlyreorientwhenthereisanavailablepartnerabletoacceptthebond,withthestrengthofthe
brokenhydrogenbondplayinglittleornorole[1135].Themolecularorbitalsofwaterindicatethatthetwo'lonepairs'of
electronsdonotgivedistinctdirectedelectrondensityinisolatedmolecules,withtetrahedralnatureofwater'shydrogen
bondingduetofourcoordinationinvolvingtwodonorandtwoacceptorhydrogenbonds.Howevertrigonal
(approximatelyplanar)hydrogenbondingisalsopossiblewithtwodonorandoneacceptorhydrogenbondsassociated
withindividualwatermolecules.Thelackofsubstantialtetrahedrallypositioned'lonepair'electronsmayeasethisprocess,
atacostofonehydrogenbondenergy.Alsotheacceptorhydrogenbondinthreecoordinatedbuttetrahedral
arrangements(twodonorandoneacceptorhydrogenbondswithonevacantacceptorsite)canslidethroughaplanar
arrangementtothevacanttetrahedralsitewithoutbreaking.Thisflexibilityinthehydrogenbondingtopologyfacilitates
hydrogenbondingrearrangements.[BacktoTop ]

Bifurcatedhydrogenbonds

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Bifurcatedhydrogenbonds,wherebothhydrogenatomsfromonewatermoleculearehydrogenbondingtothesame
otherwatermolecule,ortwohydrogenbondsfromwatermoleculesreplaceoneoriginalhydrogenbond(seeabove)or
onehydrogenatomsimultaneouslyformshydrogenbondstotwootherwatermolecules(seebelow)havejustunderhalf
thestrengthofanormalhydrogenbond(perhalfthebifurcatedbond)andpresentalowenergyrouteforhydrogen
bondingrearrangements(seeabove)[255].Theyallowtheconstant
randomizationofthehydrogenbondingwithinthenetwork.However,it
shouldbenotedthattheyoftenrequirethebreakageoftwohydrogen
bondsonehydrogenbondtoformthebifurcatedarrangementand
anothertomakewayforadifferenthydrogenbondtoform.Anynecessary
rotationmayalsoinvolvebendingorstretchingotherhydrogenbonds.
Bifurcationofhydrogenbondscannotcausetheirnetbreakagebutjust
theexchangeofhydrogenbonds[1135].Trifurcatedhydrogenbonds
(whereonehydrogenatomsimultaneouslyformshydrogenbondstothree
otherwatermolecules,formingatetrahedralface)mayalsoformbutonly
haveaboutonesixththestrengthofanormalhydrogenbondperthirdof
thebifurcatedbond[573],requirefreelonepairsonallthreeboundwater
moleculesandtherestoflocalclustermustalsobepoorlyhydrogenbonded.[BacktoTop ]

Informationtransfer
Hydrogenbondingcarriesinformationaboutsolutesandsurfacesover
significantdistancesinliquidwater.Theeffectissynergistic,directive
andextensive.Thus,inthediagramopposite,stronghydrogen
bondinginmolecule(1),causedbysolutesorsurfaces,willbe
transmittedtomolecules2and3,thento5and6andthenas
combinedpowerto8.

Theeffectisreinforcedbyadditionalpolarizationeffectsandthe
resonantintermoleculartransferofOHvibrationalenergy,mediatedby
dipoledipoleinteractionsandthehydrogenbonds[142].Reorientation
ofonemoleculeinducescorrespondingmotionsintheneighbors.

Thussolutemoleculescan'sense'(forexample,affecteachother's
solubility)eachotheratdistancesofseveralnanometersandsurfaces
mayhaveeffectsextendingtotensofnanometers.Thislongrange
correlationofmolecularorientationhasrecentlybeenconfirmedusinghyperRayleighlightscattering[152]andisa
reasonforthehighdielectricconstantofwaterandtheconsequentialreductioninthisdielectricconstantasthe
temperatureisraisedandthenumberofhydrogenbondsisreduced[239].Wherewatermoleculesarenexttoflat
hydrophobicsurfaces,andunabletoformextensiveclathratestructuring,somehydrogenbondsmustbebrokenandthe
watermoleculeswilltendtochangeorientation,fromonehydrogenbonddirectedorthogonallyawayfromthesurface(as
inclathrates)toonehydrogenbonddirectedorthogonallytowardsthesurface,inordertominimizetheenergy
requirement.Alsothewatermoleculestendtocollapseintotheirshallowenergyminimaduetoincreasednonbonded
interactions.Althoughtheremaybeaconsequentiallyincreaseddensityinthefirstwaterlayer,thesecondand
subsequentwatershellscompensatebyformingstrongerhydrogenbondsandalessdensestructure.Consequencesof
thisincludedifferentialsolvationpropertiesaffectingsurfaceabsorption.

Hydrogenbondingrearrangementoffersalowenergypathwayforthetransferofhydrogenatomsduringtautomerism,in
awaysimilartoGrotthussmechanismforhydrogeniontransport.Shownoppositeisadeninetautomerismthatcangive
risetoAdenineCytosine(mutationproducing)pairing,whichusestheraretautomerontheleft.[BacktoTop ]

Footnotes
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a1Thisistheenergy(H)requiredforbreaking

andcompletelyseparatingthebond,and
shouldequalabouthalftheenthalpyof
vaporization.OnthesamebasisS=37Jdeg
1mol1 [168].(Lowerenthalpiesforthe
hydrogenbondhavebeenreported[1369],
varyingbetween~623kJmol1,withentropies
~2946Jdeg1mol1,dependingonthe
assumptionsmade).Justbreakingthe
hydrogenbondinliquidwaterleavingthe
moleculesessentiallyinthesamepositionrequiresonlyabout25%ofthisenergyrecentlyestimatedat6.3kJmol1
[690]andonlyjustovertwicetheaveragecollisionenergy(seebelow).Ifthehydrogenbondenergyisdeterminedfrom
theexcessheatcapacityoftheliquidoverthatofsteam(assumingthatthisexcessheatcapacityisattributabletothe
breakingofthebonds)H=9.80kJmol1[274].AnumberofestimatesgivetheequivalentGatabout2kJmol1at25
C[344]howeverfromtheequilibriumcontentofhydrogenbonds(1.7mol1)itis5.7kJmol1.Thehydrogenbonding
iniceIhisabout3kJmol1strongerthanliquidwater(=28kJmol1at0K,fromlatticeenergyincludingnonbonded
interactions)andevidencedbyanabout4pmlonger,andhenceweaker,OHcovalentbond.However,thehydrogen
bondstrengthinsupercooledliquidwatermaybestrongerthaninice[2020].[Back]

a2TheaveragemolecularlineartranslationalenergyisRT/2.TheaveragecollisionenergyisRT(2.479kJmol1).2%of
collisionshaveenergygreaterthantheenergyrequiredtobreakthebonds(9.80kJmol1,[274])asdeterminedbyexcess
heatcapacity.[Back]

a3Unexpectedlyforsuchanimportantparameter,thereissomedisputeastowhetherthehydrogenbondsinD Oand
2
H2Oarelongerorshorterorthesamelength.Onereportstates(oppositetoearlierconclusions[554])thatD2Ohydrogen
bondsarelonger(HO1.74,DO1.81at23C[1485],butmorelineartheweakeningonlengtheningbeing
compensatedbythestrengtheningonstraightening)andD2Ohydrogenbondsbeingmoreasymmetric(withthe
hydrogenatommoredisplacedawayfromthecenteroftheOHObond),moretetrahedral,moreplentifuland
strongerthaninH2O[1485].MorerecentlythehydrogenbondsinD2OandH2Ohavebeenfoundtobeaboutthesame
lengthduetocompensatoryquantumeffects[1752].HydrogenbondinT2Oareexpectedtobestrongerstill.Thusgiven
thechoice,hydrogenbondsformwiththepreferenceOTO>ODO>OHO.[Back]

bUnfortunatelythisisdifficulttouseasatool,however,duetotheaveragingoftheshiftandthecomplexityofthe
system.Thespinlatticerelaxationtimes(T1,~3.6s,25C)ofthewaterprotonsisalsoafunctionofthehydrogen
bonding,beingshorterforstrongerbonding.Theeffectofsolutes,however,showsthechemicalshiftandspinlattice
relaxationtimearenotcorrelated,assolutesmayreducetheextentofhydrogenbondingatthesametimeasincreasing
itsstrength[281].Thespinlatticerelaxationtimehasbeenfoundtobetwoorthreetimesgreaterthanthespinspin
relaxationtime,suggestingthepresenceofsupramolecularstructuringinthewater[1664].[Back]

cWhetherahydrogenbondisconsideredbrokenorjuststretchedand/orbentshouldbedefinedbyitsstrengthbut,as
theisolatedbondstrengthmaybedifficulttodetermine,thisoftenremainsamatterofanarbitrarydefinitionbasedon
distancesandangles.Anarrangementwithstrainedgeometryisveryunlikelytolastlong.Itmay,however,occurduring
thebreakage,formationorpartnerswitching(thatis,bifurcation)ofahydrogenbondorarisetransiently,duetothermal
effectsorothermolecularinteractions,inalonglivedhydrogenbond.Thelifetimeofahydrogenbond(ifmorethan1013
s)presentsanothermeasureofhydrogenbondformationbutthisalsosuffersfromuncertaintiesinthedefinitionofits
geometry.Brokenhydrogenbondsdonotlastlongenoughtopresentafreehydroxyl(OH)infraredspectrum[1687].
[Back]

c2 Otherworkersusemoregenerousparametersforexample,in[848],thehydrogenbondlengthmustbelessthan3.50
andthebondanglegreaterthan120,whereasotherssuggesthydrogenbondingbasedonnearestneighbors[1432].
Theimportanceofchoosingacorrectdefinitionforthehydrogenbondshasbeenexamined[1240].Thesimpledistance
criterionof2.50fortheHOdistancewasfoundveryusefulandcheapestincomputationaltermswhereasmethods
basedonenergyprovedpoor.Addingfurthercriteria,suchasthebondangles,provedofmarginaluse[1240].Six
differenthydrogenbonddefinitionsaredescribedin[1555]wheretheyallgavethesamequalitativepictureofthe
spectroscopy.Usingsimulations,ithasbeenproposedthatpurelygeometricandenergeticdefinitionsareinaccurateas
theymayoverestimatetheconnectivityandlifetimeofhydrogenbondsandcannotdistinguishimproperrelative
orientations[1335].Suchoverestimatesmay,however,bebalancedbyunderestimatesduetothecutoffparameters.
ThedifferencebetweentheOHandHObondlengthshasalsobeensuggestedwherewater'shydrogenbondgivesa
differencewithfluctuationsaround0.75(withbondangles~155180)andthebondcanbeconsideredbrokenwith
OHHObondlengthdifferencesvaryingwiththebondangle(1801.671351.53901.40),ormoresimply
forhydrogenbondsofsignificantstrength(coveringabout99%ofwaterhydrogenbonds)aswheretheOHHObond
lengthdifferenceislessthan1.25[2025].Someofthemethodsfordefiningwater'shydrogenbondhavebeen
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comparedandreviewed[2028].[Back]

dThereisstillsomecontroversysurroundingthispartialcovalencywithbothfor(forexample,[411]givesthe3a orbital
1
asmostresponsibleforthehydrogenbondingviaorbitalmixing),against(forexample,[437]favors'antibonding'rather
thanbondingduetothechargetransfer)andneutral[438]intherecentliterature.Ifthewaterhydrogenbondis
consideredwithinthecontextofthecompleterangeofmolecularhydrogenbondingthenitappearsmostprobablethatit
isnotsolelyelectrostatic[447]indeedthedissociationofwater,theformationofthesymmetrical'Zundel'H5O2+ion,the
continuoustransformationoficeVIItoiceXandthelowerionizationpotentialforliquidwaterrelativetowatervapor
wouldallseemtoindicateacontinuityofelectronsharingbetweenwatermolecules.AlthoughNHNandNHO
hydrogenbondsareknowntobeweakerthantheOHOhydrogenbondsinwater,thereisclearevidenceforthese
bonds'covalentnaturesfromNMR.Innucleicacids,internucleotideNHNcoupling(2JNN,using15Nnuclei)confirms

somecovalentnatureintheNHNhydrogenbond[779].Also,3bondNMR(3JNC)splittinghasbeenfoundthrough
peptideNHO=Chydrogenbondsinproteins,confirmingsomecovalentnatureintheNHOhydrogenbond[780].
Thecurrentdefinitionforahydrogenbond(seehbelow)involvesthenecessityofevidenceforbondformationwhich
necessarilyrequireselectrondelocalization.Suchelectrondelocalizationinthewaterdimerhasbeenestimatedtoinvolvea
chargetransferof0.0146e[2202].[Back]

eTheOHvibrationalfrequencydoesnotfollowtheOOhydrogenbondlengthexactlyduetodispersionofthe
hydrogenbondOHOangle[439].[Back]

fHowevernotethatsomehydrogenbondsmaydistortahydrogenbondedclustersuchthatwhensuchabondbreaks
thedetachedclustermayformamoreoptimumtetrahedrallybondedarrangementwithlowerenergyandthusreclaiming
someormostoftheenergylostbybondbreakage.[Back]

gTheinterpretationofthestructureofwaterintermsofstrandsandringsofdoublylinkedhydrogenbondedmolecules
[613]wasnotconfirmedbyaComptonscatteringstudy[1083]wherethedatawasconsistentwith3.9hydrogenbonds
(Roo3.2)aroundeachwatermolecule,andhasbeendisputedbyanotherXrayabsorptionspectroscopicstudy[690a],
whichpresentsacaseforthe'non,oronlyweakly,bondedOHgroups'toformthemajorityofOHgroupspresentand
thatthesegroupsaremorestronglybonded.Also,Bowronchallengestheaboveinterpretation(thatis,[613])inthe
Discussionincludedin[746]andaRamanstudysupportsthefullytetrahedrallyhydrogenbondedmodel[875].This
disputewasthoughttohavebeenresolvedbyanabinitiomoleculardynamicsstudy[832]thatshows170fsfluctuations
of2.2foldstrengthbetweenthetwodonorhydrogenbondsfromeachwatermoleculewhilsttheoverallgeometric
connectivityisretained,inlinewiththehypothesisfirstpresentedabove.Howeverthisstudy[832]hasattractedserious
criticism[1159],leavingitsconclusionsseeminglyunproven.Recentabinitiocalculationsofthexraycrosssectionof
liquidwatershowsonly20%brokenhydrogenbondsarepresent[1059],otherabinitiocalculationsshowprimarily
tetrahedralcoordinatedwatermolecules[1654]andanovelforcefieldforwater,developedfromfirstprinciples,gives3.8
sharedtetrahedrallycoordinatedhydrogenbondsperwatermolecule[1189].Also,anabinitioquantum
mechanical/molecularmechanicsmoleculardynamicssimulationstudyshowsthatalthoughthetimeaveragedhydrogen
bondingisaboutfoursharedhydrogenbondsperwatermolecule,theinstantaneousvalueissignificantlyloweratabout
2.8sharedhydrogenbondsperwatermolecule[922].Tetrahedrallycoordinatedwaterseemsmostacceptedatthe
presenttime[2095],butitisclearthatamixtureofaminorityofhigher(4linked)andamajorityoflower(2linked)
hydrogenbondcoordinatedwatercanbefittedequallywellwiththeexperimentaldata[1350].[Back]

h Arecenthistoricalreviewofhydrogenbondingisavailable[1950].Thehydrogenbondinwaterwasfirstsuggestedby
LatimerandRodebushin1920[789].HydrogenbondsaredifferentfromvanderWaalsdispersioninteractions,butthis
differenceisblurredinsomeinstances.Thekeytothedifferenceisthathydrogenbondingusuallyinvolvespartialcovalent
bondformationandamutualpenetrationofatomswithintheirvanderWaalsradii.TheIUPACdefinitionis'Thehydrogen
bondisanattractiveinteractionbetweenahydrogenatomfromamoleculeoramolecularfragmentXHinwhichXis
moreelectronegativethanH,andanatomoragroupofatomsinthesameoradifferentmolecule,inwhichthereis
evidenceofbondformation.'[1702].Themostimportantcriteriaforahydrogenbondare:(i)theHintheXHgroupis
moreelectropositivethanXand(ii)thephysicalforcesinvolvedinhydrogenbondingshouldincludeattractiveelectrostatic
forces,i.e.itshouldnotbeprimarilydispersiveforces[1461].

Hydrogenbondsinothermolecules,suchasDNA,alsopossessconsiderablecovalentcharacter[1867].[Back]

iThevanderWaalsdispersiveattractionhasbeenestimatedashighasabout5.5kJmol1[548]basedonisoelectronic
moleculesatoptimalseparation,butislikelytoberepulsivewithinahydrogenbondduetotheclosecontact(seefor
example,[736]).Separatingthehydrogenbondcomponents,asbelow,helpsourunderstanding,althoughinrealitythese
componentsarecombined.

Hydrogenbondcontributions
Attraction/repulsion
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longrangeinteraction(<30)basedonpointcharges,orondipolesplusquadrupoles,
andsoon.Theymaybeconsideredasvaryingwithdistance1.

++electrostaticattraction

++polarizationattraction

duetonetattractiveeffectsbetweenchargesandelectronclouds(<8),whichmay
increasecooperativelydependentonthelocalenvironment.Theymaybeconsideredas
varyingwithdistance4.Thisnetattractiveeffectmaycontainasmallrepulsiveelement
duetoslightlyincreasedelectroncloudoverlap.

+covalencyattraction

highlydirectionalandincreasesonhydrogenbondedcyclicclusterformation.Itisvery
dependentonthespatialarrangementofthemoleculeswithinthelocalenvironment(<
6)

+dispersiveattraction

interaction(<6)duetocoordinatedeffectsofneighboringelectronclouds.Theymay
beconsideredasvaryingwithdistance6.

electronrepulsion

veryshortrangeinteraction(<4)duetoelectroncloudoverlap.Theymaybe
consideredasvaryingwithdistance12.
[Back]

jInanunstrainedtetrahedralnetwork(suchasiceIh)onlythesixstructuresbelowcanarisewithnostructuresat

intermediateangles.Thehydrogenbondenergydependsparticularlyontheangleofrotationaroundthehydrogenbond,
asbelow,duetotheinteractionbetweenthemoleculardipoles.Notethatthehydrogenbondsinthestructurepairs(a)
and(e),and(b)and(d)haveidenticalenergies.IniceIhwithnonetdipolemoment,theconfigurationswithextreme
cis/transratioshave56.3%cis(i.e.a+e+f)or64.7%trans(thatis,b+c+d)butthecalculateddifferenceinenergieswas
only0.12%(0.06kJmol1)[858]muchlowerthantheexpected(severalkJmol1)differenceinenergybetweenthe
limitingtransandcisstructurescandf.Asa,candeinvolveprotonsinhydrogenbondsparalleltothecaxis,their
increasedstrengthrelativetob,dandfmaybecausativetothe(0.3%)shortenedcaxisintheiceIhunitcell.

[Back]

kTheapproximatebondenergies(kJmol1)asderivedfromDOHOD inD O[1932].ThestepsinH Oarelikelytobe


2
2
2
closerto5kJmol1.[Back]

lThetetrahedralangleis180cos1(1/3)109.47122=10928'16.39".Tetrahedrality(q,theorientationalorder
parameter)maybedefinedas

,wherejkistheangleformedbylinesdrawnbetweenthe

oxygenatomsofthefournearestandhydrogenbondedwatermolecules[169].Itequalsunityforperfectlytetrahedral
bonding(wherecos(jk)=1/3)andaverageszero(0.5SD)forrandomarrangements,withaminimumvalueof3.The
densityorderparameterisdescribedelsewhere.[Back]

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ThispagewaslastupdatedbyMartinChaplinon20May,2015
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