During the next decade a tremendous advance will take place in instrumentation for spectroscopy of the interstellar medium. Major new facilities (ALMA, SOFIA, APEX, LMT, Herschel and others) will be constructed and commissioned, so that the science opportu
Phillips,Vastel:Futuremmandsubmminstrumentation7
ofsevenwhitedwarfsandsub-dwarfsleadtoaD/Hra-tioof(1.52±0.08)×10 5(Moosetal.2002),tobecomparedwiththevalueof(1.5±0.1)×10 5(Lin-sky1998)determinedfromHSTobservationsoflate-typestars.Bothmeasurementsrefertowarminterstellargas,locatedwithin100pcoftheSun.However,di erencesbyafactoroftwohavebeenderivedfromCopernicusandHSTdatatowardstarslocatedbetween100and500pcfromtheSun.Theratioseemsconstantwithin100pc,butseemstovaryatconsiderablygreaterdistances.Thereisnoidenti edprocesswhichcanexplainsuchlargevariabilityandwithoutanunderstandingitisnotjusti- edtouseanaverageD/Hratiotorepresenttheprimor-dialdeuteriumabundance.Wewillargue,below,thatthechemistryoftheinterstellarmediumcouldberesponsi-ble,inthatitcanextractlargeamountsofdeuteriumwhichbecomestrappedinmoleculesandongrains.
4.1.BasicChemistry
Deuteriumbearingspeciesaregoodprobesofthecoldphasesofmolecularcloudspriortostarformationandmanyrecentobservationspointtothefactthattheirabundancerelativetotheirhydrogenatedanaloguesarelarger,byafactorupto10000,thanthesolarneighbor-hoodvalueof~1.5×10 5(seereferencesabove).
Thereforetherelativeabundanceofisotopomersdoesnotmeasuretherelativeabundancesoftheisotopesthem-selves.Thechemicalfractionationprocessarisesfromdif-ferencesinthemolecularbindingenergiescausedbythedi erentzero-pointvibrationenergy.Almostincredibly,thiscanleadtoadetectablequantityofthetriplydeuter-atedammonia(seesection4.2).
Inmolecularclouds,hydrogenanddeuteriumarepre-dominantlyintheformofH2andHDrespectively.SotheHD/H2ratioshouldcloselyequaltheD/Hratio.Sincethezero-pointenergiesofHDandH2di ergreatly(seeFigure7),thechemicalfractionationwillfavorthepro-ductionofHDcomparedtoH2.
DeuteriumisinitiallyremovedfromtheatomicphasethroughchargeexchangewithH+,followedbyreactionwiththeabundantH2.HDcouldfurtherinteractwithD+againtogiveD2:H++D←→H+D+(1)D++H2←→HD+H++ E1(2)D++HD←→D2+H++ E2(3)
Thereactions2and3areexothermicassubstitutinganHatomversusanDatominapolyatomicmolecule
generallyleadstoagaininenergy.Theseenergiesmaybecomputed(at0K)bythedi erencesbetweenthezero-pointenergiesoftheproductsandthereactants.Theen-ergies E1and E2arequotedin gure7.
separation
H
HD Ε ~ 410 Κ1D
Ε ~ 500 Κ2
Figure7.H2,HDandD2potentialenergydiagram. Ei
isthedi erencebetweenthezeropointenergiesrelativetotheminimumofthemolecularpotentialcurve.Inthedense,coldregionsoftheinterstellarmedium,Dwillbeinitiallynearlyallabsorbed+intoHD.Theabun-dantionavailableforinteractionisH3,whichgivesH2D+
:
H+3+HD←→H2D++H2+ E3
(4)
where E3/k~230Kforatypicaltemperatureofadarkcloudofabout10K(e.g.Millaretal.1989).Thereversereactiondoesnotoccure cientlyinthecolddensecloudswhereobviouslythetemperatureismuchlowerthan E3.Therefore,thedegreeoffractionationofH2D+becomesnon-negligible.
Thisprimaryfractionationcanthengiverisetoasecondfractionation:
H2D++CO←→DCO++H2
(5)←→HCO++HD
(6)IndarkcloudsH+3givesrisetoHCO+
viathereaction:
H++3+CO←→HCO+H2
(7)
4.2.MultiplyDeuteratedMoleculesThestudyofdoublydeuteratedinterstellarmoleculeshasbeenboominginthelastfewyearssincethesurprisingdiscoveryofalargeamount(~5%)ofdoublydeuteratedformaldehydeinthelowmassprotostarIRAS16293-2422(Ceccarellietal.1998,Loinardetal.2000).ThisismorethanoneorderofmagnitudehigherthaninOrionKLwhereD2COwas rstdetectedbyTurner(1990).This
Energy