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1 1 APPENDIX A: CHEMICAL NEWORK In ables A1 A1 we list the chemical reactions included in our model of primordial gas, along with the rate coefficients adopted and the references from which these rate coefficients were taken. Some of these reactions are discussed in more detail in Section 3.1. In these tables, is the gas temperature in K, 3 = /300 K, and e is the gas temperature in units of ev.

2 able A1. Chemical processes: collisional ionization (CI. No. Reaction Rate coefficient (cm 3 s 1 Ref. CI1 H + e H + + e + e k CI1 = exp[ ln e (ln e (ln e (ln e (ln e (ln e (ln e (ln e 8 ] CI D + e D + + e + e k CI = k CI1 1 CI3 He + e Hep + e + e k CI3 = exp[ ln e (ln e (ln e (ln e (ln e (ln e (ln e (ln e 8 ] CI Li + e Li + + e + e k CI = exp 700 Notes: is the gas temperature in K, 3 = /300 K, and e is the gas temperature in ev. References: 1 Janev et al.(1987; Voronov (1997. able A. Chemical processes: photorecombination (PR. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. ( PR1 H + + e H + γ k PR1 = ( [ ]. 1 PR D + + e D + γ k PR = k PR1 1 PR3 Hep + e He + γ k PR3,rr,A = [ log Case A 0.31(log (log 3] k PR3,rr,B = [ log Case B 0.85(log [ (log ( 3] k PR3,di = ( 5500 exp exp ( ] ( exp [ ( ] PR Li + + e Li + γ k PR,rr = [ ( ] [ ( k PR,di = ( 3500 exp exp ( ] exp Notes: is the gas temperature in K. Note that the recently revised values for PR1 and for the radiative recombination portions of PR3 and PR presented by Badnell (00b do not differ from the older rate coefficients quoted here by more than a couple of percent at the temperatures of interest in this study. References: 1 Ferland et al. (199; Hummer & Storey (1998; 3 Badnell (00a; Verner & Ferland (199; 5 Bautista & Badnell (007.

3 3 able A3. Chemical processes: dissociative recombination (DR. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. DR1 Htp + e H + H k DR1 = K 1 = > 17 K DR HD + + e H + D k DR = DR3 D + + e D + D k DR3 = DR H e Ht + H k DR = DR5 H e H + H + H k DR5 = DR H D + + e H + H + D k DR = DR7 H D + + e Ht + D k DR7 = DR8 H D + + e H + HD k DR8 = DR9 HD + + e D + D + H k DR9 = DR10 HD + + e D + H k DR10 = DR11 HD + + e HD + D k DR11 = DR1 D e D + D k DR1 = DR D e D + D + D k DR = DR1 HeH + + e He + H k DR1 = DR15 HeD + + e He + D k DR15 = DR1 He + + e He + He k DR1 = DR17 LiH + + e Li + H k DR17 = DR18 LiD + + e Li + D k DR18 = DR19 LiH + + e Li + Ht k DR19 = DR0 LiH + + e LiH + H k DR0 = DR1 LiH + + e Li + H + H k DR1 = Notes: is the gas temperature in K, and 3 = /300 K. References: 1 Schneider et al. (199; Stromhölm et al. (1995; 3 Walmsley et al. (00; McCall et al. (00; 5 Larsson et al. (199; Roberts et al. (00, based on Larsson et al. (199; 7 Larsson et al. (1997; 8 Guberman (199; 9 Stancil et al. (1998, based on Guberman (199; 10 Carata et al. (1999; 11 Krohn et al. (001; 1 same as corresponding H reaction; homas et al. (00, C. Greene (private communication.

4 able A. Chemical processes: charge transfer (C. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. ( C1 H + D + D + H + k C1 = exp C H + D D + H k C = C3 H + Htp Ht + H + k C3 = C H + HD + HD + H + k C = C5 H + D + D + H + k C5 = C H + Hep He + H + + γ k C = C7 H + He + He + He + H+ k C7 = C8 H + LiH + LiH + H + k C8 = exp C9 H + LiD + LiD + H + k C9 = exp 7900 C10 D + H + H + D + k C10 = exp C11 D + H H + D k C11 = C1 D + Htp Ht + D + k C1 = C D + HD + HD + D + k C = C1 D + D + D + D + k C1 = C15 D + Hep He + D + + γ k C15 = C1 D + He + He + He + D+ k C1 = C17 D + LiH + LiH + D + k C17 = exp 7900 C18 D + LiD + LiD + D + k C18 = exp 7900 C19 Ht + H + H + Htp k C19 = [ ln (ln (ln (ln (ln (ln (ln 7 ] 7.15 exp C0 Ht + D + D + Htp k C0 = k C19 C1 Ht + Hep He + Htp k C1 = C Ht + Hep He + H + H + k C = exp ( 35 1 C HD + H + H + HD + k C = k C19 C5 HD + D + D + HD + k C5 = k C19 C HD + Hep He + HD + k C = ( C3 Ht + Li + Li + Htp k C3 = exp ( C7 HD + Hep He + H + + D k C7 = exp ( C8 HD + Hep He + H + D + k C8 = exp C9 HD + Li + Li + HD + k C9 = k C3 C30 D + H + H + D + k C30 = k C19 C31 D + D + D + D + k C31 = k C19 C3 D + Hep He + D + k C3 = C33 D + Hep He + D + + D k C33 = C3 D + Li + Li + D + k C3 = k C3 ( C35 He + H + H + Hep k C35 = exp K 15 = > K C3 He + D + D + Hep k C3 = k C35 11

5 5 able A continued No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. ( C37 Li + H + H + Li + k C37 = exp C38 Li + H + H + Li + + γ k C38 = exp C39 Li + D + D + Li + k C39 = exp C0 Li + D + D + Li + + γ k C0 = exp C1 Li + Htp Ht + Li + k C1 = C Li + HD + HD + Li + k C = k C1 C3 Li + D + D + Li + k C3 = k C1 C LiH + H + H + LiH + k C = C5 LiH + D + D + LiH + k C5 = C LiD + H + H + LiD + k C = C7 LiD + D + D + LiD + k C7 = Notes: is the gas temperature in K, and 3 = /300 K. References: 1 Savin (00; Dalgarno & McDowell (195, scaled by D reduced mass; 3 Karpas, Anicich & Huntress (1979; same as corresponding H reaction; 5 Zygelman et al. (1989; Estimate by Stancil et al. (1998, based on Stancil et al. (1993; 7 Stancil et al. (199; 8 Zygelman et al. (1989, scaled by D reduced mass; 9 As ref., but scaled by D reduced mass; 10 Savin et al. (00; 11 Barlow (198; 1 Estimate, based on low-energy extrapolation of cross-section in Wutte et al. (1997; total rate coefficient from Barlow (198, branching ratios from Pineau des Forets et al. (1989; 1 Walmsley, Flower, & Pineau des Forets (00; 15 Kimura et al. (1993; 1 Kimura, Dutta, & Shimakura (199; 17 Stancil & Zygelman (199; 18 Kimura, Dutta & Shimakura (199, scaled by D reduced mass; 19 Stancil & Zygelman (199, scaled by D reduced mass; 0 From detailed balance applied to inverse reaction; 1 Bodo et al. (001.

6 able A5. Chemical processes: radiative attachment and radiative association (RA. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. RA1 H + e H + γ k RA1 = dex[ log 000 K (log 0.037(log 3 ] = dex[ (log > 000 K (log (log ] RA D + e D + γ k RA = k RA1 1 RA3 H + H + Htp + γ k RA3 = dex[ log (log 0.19(log 3 ] RA H + D + HD + + γ k RA = exp 3 RA5 H + D HD + γ k RA5 = 10 5 [ ln 10 < 00 K (ln (ln (ln (ln 5] = 10 5 exp [ ln > 00 K (ln 1.19(ln (ln (ln 5] RA H + Htp H γ k RA = exp 5 RA7 H + HD + H D + + γ k RA7 = exp ( RA8 H + D + HD+ + γ k RA8 = exp ( RA9 H + Hep HeH + + γ k RA9 = exp RA10 H + Li + LiH + + γ k RA10 = dex [ log (log ] ( RA11 D + H + HD + + γ k RA11 = exp ( RA1 D + D + D + + γ k RA1 = exp ( RA D + Htp H D + + γ k RA = exp ( RA1 D + HD + HD + + γ k RA1 = exp ( RA15 D + D + D+ 3 + γ k RA15 = exp ( RA1 D + Hep HeD + + γ k RA1 = exp ( 8700 RA17 D + Li + LiD + + γ k RA17 = exp 7000 RA18 Ht + H + H γ k RA18 = RA19 Ht + D + H D + + γ k RA19 = RA0 Li + + Ht LiH + + γ k RA0 = RA1 HD + H + H D + + γ k RA1 = RA HD + D + HD + + γ k RA = RA3 D + H + HD + + γ k RA3 = RA D + D + D γ k RA = ( RA5 He + H + HeH + + γ k RA5 = exp ( 000 RA He + D + HeD + + γ k RA = exp ( 000 RA7 He + Hep He + + γ k RA7 = exp ( 1 RA8 Li + e Li + γ k RA8 = exp RA9 Li + H + LiH + + γ k RA9 = RA30 Li + D + LiD + + γ k RA30 =. 10 { RA31 Li + H LiH + γ k RA31 = [0.057(/ (/ ] 1} RA3 Li + D LiD + γ k RA3 = exp ( 3300 Notes: is the gas temperature in K, and 3 = /300 K. References: 1 Wishart (1979; Ramaker & Peek (197; 3 Ramaker & Peek (197 and Frommhold & Pickett (1978, scaled by D reduced mass; Dickinson (005; 5 Dalgarno & McDowell (195; Same as corresponding H reaction, but scaled by D reduced mass; 7 Kraemer, Špirko & Ju?rek (1995; 8 Dalgarno et al. (199; Gianturco & Gori Giorgi (199; 9 Stancil et al. (199, scaled by D reduced mass; 10 Gerlich & Horning (199; 11 estimate, based on Gerlich & Horning (199: highly uncertain; 1 estimate - see also Section ; Juřek, Špirko & Kraemer (1995; 1 Stancil et al. (1993; 15 Ramsbottom et al. (199; 1 Dalgarno et al. (199; 17 Bennett et al. (

7 7 able A. Chemical processes: associative detachment, dissociative attachment and associative ionization (AD. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. AD1 H + H Ht + e k AD1 = AD D + H HD + e k AD = AD3 H + D HD + e k AD3 = AD D + D D + e k AD = AD5 Ht + e H + H k AD5 = exp AD HD + e H + D k AD = exp 3000 AD7 HD + e D + H k AD7 = exp 3000 AD8 D + e D + D k AD8 = exp 3000 AD9 H + + H Htp + e k AD9 = K 5 = > 8000 K AD10 H + + D HD + + e k AD10 = AD11 D + + H HD + + e k AD11 = AD1 D + + D D + + e k AD1 = AD Htp + H H e k AD = exp 3100 AD1 Htp + D H D + + e k AD1 = exp 300 AD15 HD + + H H D + + e k AD15 = exp 3100 AD1 HD + + D HD + + e k AD1 = exp 3100 AD17 D + + H HD + + e k AD17 = exp 3100 AD18 D + + D D e k AD18 = exp 3100 AD19 Li + H LiH + e k AD19 = AD0 Li + D LiD + e k AD0 = AD1 Li + H LiH + e k AD1 = AD Li + D LiD + e k AD = Notes: is the gas temperature in K, and 3 = /300 K. References: 1 Launay et al. (1991; Same as corresponding H reaction, but scaled by D reduced mass; 3 Schulz & Asundi (197; Xu & Fabrikant (001; 5 Poulaert et al. (1978; Naji et al. (1998; 7 Stancil et al. (199.

8 8 able A7. Chemical processes: collisional detachment and collisional dissociation (CD. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. CD1 H + e H + e + e k CD1 = exp[ ln e (ln e (ln e (ln e (ln e (ln e (ln e (ln e 8 ] CD H + H H + H + e k CD = e e 0.1 ev 1 = exp[ e > 0.1 ev ln e (ln e (ln e (ln e (ln e (ln e (ln e (ln e (ln e 9 ] CD3 H + D H + D + e k CD3 = k CD CD H + He H + He + e k CD = exp CD5 D + e D + e + e k CD5 = k CD1 CD D + H D + H + e k CD = k CD CD7 D + D D + D + e k CD7 = k CD CD8 D + He D + He + e k CD8 = exp CD9 Ht + H H + H + H k CD9 = exp ( v=0 5 = k B1 /K LE CD10 Ht + Ht H + H + Ht k CD10 = ( exp 557. v = 0 7 = k B /K ] LE CD11 Ht + He H + H + He k CD11 = dex log 987 v = 0 8 = exp 5000 LE 9 CD1 Ht + e H + H + e k CD1 = exp v = 0 10 = exp LE 10 CD HD + H H + D + H k CD = k CD9 See?? CD1 HD + Ht H + D + Ht k CD1 = k CD10 See?? CD15 HD + He H + D + He k CD15 = k CD11 See?? CD1 HD + e H + D + e k CD1 = exp v = 0 11 = exp LE 11 CD17 D + H D + D + H k CD17 = k CD9 CD18 D + Ht D + D + Ht k CD18 = k CD10 CD19 D + He D + D + He k CD19 = k CD11 CD0 D + e D + D + e k CD0 = exp v = 0 10 = exp LE 10 CD1 LiH + + D Li + + H + D k CD1 = exp CD LiH + + D Li + H + + D k CD = exp CD3 LiH + + D Li + H + D + k CD3 = exp CD LiD + + D Li + + D + D k CD = exp CD5 LiD + + D Li + D + + D k CD5 = exp CD LiH + + Ht Li+ + Ht + Ht k CD = exp 3000 Notes: is the gas temperature in K and e is the gas temperature in ev. K is the equilibrium constant relating reactions B1 and CD9, and reactions B and CD10; its value is given in??. References: 1 Janev et al. (1987; Assumed same as corresponding H reaction; 3 Huq et al. (198; Same as corresponding H reaction, but scaled by D reduced mass; 5 Mac Low & Shull (198; determined from three-body rate coefficient by detailed balance (see Section 3.1.7; 7 Martin, Keogh, & Mandy (1998; 8 Dove et al. (1987; 9 determined from the Walkauskas & Kaufman (1975 rate coefficient for reaction B3 by detailed balance; 10 revisan & ennyson (00a; 11 revisan & ennyson (00b; estimate see also Section

9 9 able A8. Chemical processes: mutual neutralization (MN. No. Reaction Rate coefficient (cm 3 s 1 Ref. MN1 H + + H H + H ( k MN1 =. 10 1/ MN D + + H D + H k MN = 1.1 k MN1 MN3 H + + D D + H k MN3 = 1.1 k MN1 MN D + + D D + D k MN = 1.3 k MN1 MN5 Htp + H Ht + H k MN5 = MN Htp + H H + H + H k MN = MN7 Htp + D Ht + D k MN7 = MN8 Htp + D H + H + D k MN8 = MN9 HD + + H HD + H k MN9 = MN10 HD + + H D + H + H k MN10 = MN11 HD + + D HD + D k MN11 = MN1 HD + + D D + H + D k MN1 = MN D + + H D + H k MN = MN1 D + + H D + D + H k MN1 = MN15 D + + D D + D k MN15 = MN1 D + + D D + D + D k MN1 = MN17 H H Ht + H + H k MN17 = MN18 H H Ht + Ht k MN18 = MN19 H D Ht + H + D k MN19 = MN0 H D Ht + HD k MN0 = MN1 H D + + H Ht + H + D k MN1 = MN H D + + H Ht + HD k MN = MN3 H D + + H HD + H + H k MN3 = MN H D + + D Ht + D + D k MN = MN5 H D + + D Ht + D k MN5 = MN H D + + D HD + H + D k MN = MN7 H D + + D HD + HD k MN7 = MN8 HD + + H Ht + D k MN8 = MN9 HD + + H HD + H + D k MN9 = MN30 HD + + H HD + HD k MN30 = MN31 HD + + H D + H + H k MN31 = MN3 HD + + D HD + D + D k MN3 = MN33 HD + + D HD + D k MN33 = MN3 HD + + D D + H + D k MN3 = MN35 D H HD + D k MN35 = MN3 D H D + H + D k MN3 = MN37 D D D + D + D k MN37 = MN38 D D D + D k MN38 = MN39 Hep + H He + H k MN39 = exp 7 00 MN0 Hep + D He + D k MN0 = exp 00 MN1 Li + + H Li + H k MN1 = exp MN Li + + D Li + D k MN = exp MN3 Li + H + Li + H k MN3 = exp MN Li + D + Li + D k MN = exp Notes: is the gas temperature in K, and 3 = /300 K. Some of the mutual neutralization reactions listed here also include dissociation or transfer in the process. References: 1 Croft et al. (1999; Same as corresponding H reaction, but scaled by D reduced mass; 3 Dalgarno & Lepp (1987; Dalgarno & McDowell (195; 5 Le euff et al. (000; As, with the additional assumption of equally probable outcomes; 7 Peart & Hayton (199.

10 10 able A9. Chemical processes: three-body association (B. No. Reaction Rate coefficient (cm s 1 Ref. B1 H + H + H Ht + H See?? B H + H + Ht Ht + Ht See?? B3 H + H + He Ht + He k B3 = B H + D + H HD + H See?? B5 H + D + Ht HD + Ht See?? B H + D + He HD + He k B = B7 D + D + H D + H See?? B8 D + D + Ht D + Ht See?? B9 D + D + He D + He k B9 = B10 H + + H + H Htp + H k B10 = B11 D + + H + H HD + + H k B11 = B1 H + + D + H HD + + H k B1 = B D + + D + H D + + H k B = B1 H + + Ht + H H H k B1 = B15 H + + Ht + Ht H Ht k B15 = B1 H + + Ht + He H He k B1 = B17 D + + Ht + H H D + + H k B17 = B18 D + + Ht + Ht H D + + Ht k B18 = B19 D + + Ht + He H D + + He k B19 = B0 H + + HD + H H D + + H k B0 = B1 H + + HD + Ht H D + + Ht k B1 = B H + + HD + He H D + + He k B = B3 D + + HD + H HD + + H k B3 = B D + + HD + Ht HD + + Ht k B = B5 D + + HD + He HD + + He k B5 = B H + + D + H HD + + H k B = B7 H + + D + Ht HD + + Ht k B7 = B8 H + + D + He HD + + He k B8 = B9 D + + D + H D H k B9 = B30 D + + D + Ht D Ht k B30 = B31 D + + D + He D He k B31 = B3 Li + H + H LiH + H k B3 = B33 Li + H + Ht LiH + Ht k B33 = B3 Li + D + H LiD + H k B3 = B35 Li + D + Ht LiD + Ht k B35 = Notes: is the gas temperature in K. References: 1 Walkauskas & Kaufman (1975; Same as corresponding H reaction; 3 Krstić, Janev, & Schultz (003; Estimate; 5 Gerlich & Horning (199; Mizusawa, Omukai, & Nishi (005.

11 11 able A10. Chemical processes: isotopic exchange (IX. No. Reaction Rate coefficient (cm 3 s 1 Notes Ref. IX1 Htp + D HD + + H ( k IX1 = exp IX Htp + D HD + H + k IX = IX3 HD + + H Htp + D k IX3 = exp 15 3 IX HD + + H Ht + D + k IX = IX5 HD + + D D + + H k IX5 = IX HD + + D D + H + k IX = IX7 D + + H HD+ + D k IX7 = exp 7 IX8 D + + H HD + D+ k IX8 = IX9 Ht + D + HD + H + k IX9 = log (log IX10 Ht + D + HD + + H k IX10 = ] exp IX11 HD + H + Ht + D + k IX11 = exp 88 5 IX1 HD + H + Htp + D k IX1 = exp 100 IX HD + D + D + H + k IX = IX1 HD + D + D + + H k IX1 = ] exp IX15 D + H + HD + D + k IX15 = exp 91 IX1 D + H + HD + + D k IX1 = ] exp IX17 Ht + D HD + H k IX17 = dex [ log 000 K (log +.509(log (log (log 5] = exp 507 > 000 K IX18 HD + H Ht + D k IX18 = exp K 8 = exp > 00 K IX19 HD + D D + H k IX19 = exp 30 8 IX0 D + H HD + D k IX0 = dex [ log 00 K (log.09(log (log (log 5] = exp 595 > 00 K 3 IX IX1 IX H D H D + + H H D + + H H + + D k IX1 = k = exp IX3 H D + + D HD + + H k IX3 = IX HD + + H H D + + D k IX = exp 00 IX5 HD + + D D+ 3 + H k IX5 = IX D H HD+ + D k IX = exp 55 IX7 H HD H D + + Ht k IX7 = IX8 H D H D + + HD k IX8 = IX9 H D HD + + Ht k IX9 = IX30 H D + + Ht H HD k IX30 = exp 3 IX31 H D + + HD H D k IX31 = exp IX3 H D + + HD HD + + Ht k IX3 = IX33 H D + + D HD + + HD k IX33 = IX3 H D + + D D Ht k IX3 = IX35 HD + + Ht H+ 3 + D k IX35 = exp 30.

12 1 able A10 continued No. Reaction Rate coefficient (cm 3 s 1 ( Notes Ref. IX3 HD + + Ht H D + + HD k IX3 = 1.0 [ exp ( 187. ] exp ( 87 IX37 HD + + HD H D + + D k IX37 = 1.0 [ exp ( 108. ] exp 8.5 IX38 HD + + HD D+ 3 + Ht k IX38 = IX39 HD + + D D HD k IX39 = ( 1 IX0 D Ht H D + + D k IX0 = exp ( 3. IX1 D Ht HD+ + HD k IX1 = exp ( 33.8 IX D HD HD+ + D k IX = 3.75 [ exp ( 155 ( ] exp exp 8 IX3 HeH + + D HeD + + H k IX3 = ( 3 IX HeD + + H HeH + + D k IX = exp 8 3 IX5 LiH + + D LiD + + H k IX5 = ( IX LiD + + H LiH + + D k IX = exp Notes: is the gas temperature in K, and 3 = /300 K. References: 1 Linder, Janev & Botero (1995; estimate; 3 Dalgarno & McDowell (195, scaled as in Stancil et al. (1998; Walmsley, Flower & Pineau des Forêts (00; 5 Gerlich (198; Our fits to cross-sections from Wang & Stancil (00; 7 Our fits to Mielke et al. (003; 8 Shavitt (1959; 9 Millar, Bennett & Herbst (1989; 10 Pineau des Forêts et al. (1989; 11 Moyano & Collins (003; 1 Derived from forward reaction, using equilibrium constant from Ramanlal & ennyson (00; Flower, Pineau des Forêts & Walmsley (00; 1 Derived from inverse reaction in Walmsley, Flower & Pineau des Forêts (00.

13 able A11. Chemical processes: transfer reactions (R. No. Reaction Rate coefficient (cm 3 s 1 Ref. R1 Htp + Ht H H ( k R1 = exp 00 1 R Htp + HD H D k R = R3 Htp + HD H D + + H k R3 = R Htp + D H D + + D k R = R5 Htp + D HD + + H k R5 = R HD + + Ht H D k R = 0.5 k R1 1 R7 HD + + Ht H D + + H k R7 = 0.5 k R1 1 R8 HD + + HD H D + + D k R8 = R9 HD + + HD HD + + H k R9 = R10 HD + + D HD + + D k R10 = R11 HD + + D D H k R11 = R1 D + + Ht H D + + D k R1 = R D + + Ht HD+ + H k R = R1 D + + HD HD+ + D k R1 = R15 D + + HD D+ 3 + H k R15 = R1 D + + D D D k R1 = R17 H H Htp + Ht k R17 = exp 1750 R18 H D Htp + HD k R18 = 0.5 k R17 5 R19 H D HD+ + Ht k R19 = 0.5 k R17 5 R0 H D + + H Htp + HD k R0 = 0.5 k R17 5 R1 H D + + H HD + + Ht k R1 = 0.5 k R17 5 R H D + + D Htp + D k R = k R17 5 R3 H D + + D HD + + HD k R3 = k R17 5 R H D + + D D + + Ht k R = k R17 5 R5 HD + + H Htp + D k R5 = k R17 5 R HD + + H HD+ + HD k R = k R17 5 R7 HD + + H D+ + Ht k R7 = k R17 5 R8 HD + + D HD+ + D k R8 = 0.5 k R17 5 R9 HD + + D D+ + HD k R9 = 0.5 k R17 5 R30 D H HD+ + D k R30 = 0.5 k R17 5 R31 D H D+ + HD k R31 = 0.5 k R17 5 R3 D D D+ + D k R3 = k R17 5 R33 He + Htp HeH + + H k R33 = exp 717 R3 He + HD + HeH + + D k R3 = k R33 7 R35 He + HD + HeD + + H k R35 = k R33 7 R3 He + D + HeD+ + D k R3 = k R33 8 R37 HeH + + H Htp + He k R37 = exp R38 HeH + + D HD + + He k R38 = exp R39 HeH + + Ht H He k R39 = exp R0 HeH + + HD H D + + He k R0 = exp 1800 R1 HeH + + D HD + + He k R1 = exp R HeD + + H HD + + He k R = exp R3 HeD + + D D + + He k R3 = exp R HeD + + Ht H D + + He k R = exp 1800 R5 HeD + + HD HD + + He k R5 = exp R HeD + + D D He k R = exp R7 LiH + + H Li + + Ht k R7 = R8 LiH + + D Li + + HD k R8 = R9 LiD + + H Li + + HD k R9 = R50 LiD + + D Li + + D k R50 = R51 LiH + + H Li + Htp k R51 = exp 00 1 R5 LiH + + D Li + HD + k R5 = k R51 R53 LiD + + H Li + HD + k R53 = k R51 1 R5 LiD + + D Li + D + k R5 = k R51 1

14 1 able A11 continued No. Reaction Rate coefficient (cm 3 s 1 Ref. R55 LiH + H + Li + + Ht k R55 = R5 LiH + D + Li + + HD k R5 = R57 LiD + H + Li + + HD k R57 = R58 LiD + D + Li + + D k R58 = R59 LiH + H + Li + Htp k R59 = R0 LiH + D + Li + HD + k R0 = R1 LiD + H + Li + HD + k R1 = R LiD + D + Li + D + k R = R3 LiH + H Li + Ht k R3 = R LiH + D Li + HD k R = R5 LiD + H Li + HD k R5 = R LiD + D Li + D k R = Notes: is the gas temperature in K, and 3 = /300 K. References: 1 Linder, Janev & Botero (1995; Stancil et al. (1998; 3 Walmsley, Flower & Pineau des Forêts (00; Sidhu, Miller & ennyson (199; 5 estimate, based on Sidhu, Miller & ennyson (199; Black (1978; 7 Stancil et al. (1998, based on Black (1978; 8 estimate, based on Black (1978; 9 Linder, Janev & Botero (1995, scaled as in Stancil et al. (1998; 10 Estimate, based on Stancil et al. (1998; 11 Same as corresponding H reaction, but scaled by D reduced mass; 1 Stancil et al. (199; Stancil et al. (1998, based on corresponding H reaction in Stancil et al. (199; 1 estimate, based on Stancil et al. (199; 15 Bodo et al. (001; 1 same as corresponding H reaction; 17 Defazio et al. (005.

15 15 able A1. Chemical processes: background radiation induced photodetachment, photodissociation and photoionization (BP. No. Reaction Rate (J 1 1 s 1 Ref. BP1 H + γ H + e R BP1 = BP D + γ D + e R BP = BP3 Htp + γ H + H + R BP3 = BP HD + + γ H + D + R BP = BP5 HD + + γ D + H + R BP5 = BP D + + γ D + D+ R BP = BP7 Ht + γ H + H R BP7 = f sh,ht 5 BP8 HD + γ H + D R BP8 = f sh,hd BP9 D + γ D + D R BP9 = BP10 H γ Htp + H R BP10 = BP11 H γ Ht + H+ R BP11 = BP1 H D + + γ Htp + D R BP1 = BP H D + + γ Ht + D + R BP = BP1 H D + + γ HD + + H R BP1 = BP15 H D + + γ HD + H + R BP15 = BP1 HD + + γ HD+ + D R BP1 = BP17 HD + + γ HD + D+ R BP17 = BP18 HD + + γ D+ + H R BP18 = BP19 HD + + γ D + H + R BP19 = BP0 D γ D+ + D R BP0 = BP1 D γ D + D + R BP1 = BP HeH + + γ He + H + R BP = BP3 HeD + + γ He + D + R BP3 = BP He + + γ He + Hep R BP = BP5 Li + γ Li + + e R BP5 = BP Li + γ Li + e R BP = BP7 LiH + + γ Li + + H R BP7 = BP8 LiH + + γ Li + H + R BP8 = BP9 LiD + + γ Li + + D R BP9 = BP30 LiD + + γ Li + D + R BP30 = BP31 LiH + γ Li + H R BP31 = BP3 LiD + γ Li + D R BP3 = Notes: γ represents a photon from the external background radiation field. he listed reaction rates were computed assuming that this background has the spectrum of a 10 5 K diluted black-body, cut-off above hν =. ev, as described in Section 3. With this spectrum, reactions with threshold energies greater than. ev do not occur and are not listed in the table. f sh,ht and f sh,hd are the self-shielding factors for Ht and HD photodissociation, respectively (see e.g. Glover & Jappsen 007. Note that in this paper, we consider only the limiting cases f sh,ht = f sh,hd = 0 and f sh,ht = f sh,hd = 1. References: 1 Wishart (1979; assumed same as for corresponding H reaction; 3 Dunn (198; total rate assumed same as for corresponding H reaction, individual outcomes assumed equally probable; 5 Draine & Bertoldi (199; Abgrall & Roueff (00; 7 estimate; 8 van Dishoeck (1988; 9 estimate, based on van Dishoeck (1988; 10 Roberge & Dalgarno (198; 11 Stancil (199; 1 Verner & Ferland (199; Galli & Palla (1998; 1 Kirby & Dalgarno (1978.

16 1 able A. Chemical processes: cosmic ray ionization (CR. No. Process Rate (ζ i /ζ H Reference CR1 H + C.R. H + + e 1.0 CR Ht + C.R. Htp + e.09 1 CR3 Ht + C.R. H + H + + e CR Ht + C.R. H + H 3. 1 CR5 He + C.R. Hep + e CR D + C.R. D + + e 1.0 CR7 HD + C.R. HD + + e.09 CR8 HD + C.R. H + D + + e 0.0 CR9 HD + C.R. H + + D + e 0.0 CR10 HD + C.R. H + D 3. CR11 D + C.R. D + + e.09 CR1 D + C.R. D + D + + e 0.09 CR D + C.R. D + D 3. Notes: C.R. represents a cosmic ray. ζ H, the cosmic ray ionization rate of atomic hydrogen, is an adjustable parameter in our models. References: 1 Walmsley, Flower, & Pineau des Forêts (00; assumed same as corresponding H process. able A1. Chemical processes: cosmic ray induced photodetachment, photodissociation and photoionization (CP. No. Reaction σ X,eff,Ht (Mb σ X,eff,H (Mb Ref. CP1 H + γ cr H + e CP D + γ cr D + e CP3 Htp + γ cr H + H CP HD + + γ cr H + D CP5 HD + + γ cr D + H CP D + + γcr D + D CP7 Li + γ cr Li + + e CP8 Li + γ cr Li + e CP9 He + + γcr He + Hep CP10 LiH + + γ cr Li + H CP11 LiD + + γ cr Li + D Notes: γ cr represents a secondary photon, produced by cosmic-ray induced excitation of H or Ht, as described in Section 3.3. he references listed are the sources from which we have taken our photodissociation or photoionization cross-sections. he emission probabilities P Ht (ν used to calculate σ X,eff,Ht are rough estimates based on the emission spectra given in Sternberg, Dalgarno, & Lepp (1987 and are likely accurate only to within a factor of a few. References: 1 Wishart (1979; assumed same as for corresponding H reaction; 3 Dunn (198; Verner & Ferland (199; 5 order of magnitude estimate; estimate, based on Stancil (199; 7 rough estimate, based on thermal rate in Galli & Palla (1998.