G4(MP2)-6X: A Cost-Effective Improvement to G4(MP2)

Transcript

1 Supporting Information For: G4(MP2)-6X: A Cost-Effective Improvement to G4(MP2) Bun Chan,* Jia Deng and Leo Radom* School of Chemistry and ARC Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, NSW 2006, Australia 32 PAGES S1

2 The g4mp2-6x Script The script g4mp2-6x is written in Perl. When it operates on Gaussian 09 output files that are associated with inputs of a particular predefined format, it returns the number of imaginary frequencies, and G4(MP2)-6X vibrationless energies and enthalpies at 0 and 298 K in Hartree for each file. It also performs checking on each file for normal termination of the calculation, as well as near linearity of the molecule, which may cause problems in the evaluation of rotational thermal contributions. A brief help page is available when one enters g4mp2-6x at the command line without any argument. An example of an appropriate Gaussian 09 input file is given below: %chk=h2.chk # BMK/6-31G(2df,p) Opt Hydrogen molecule G4(MP2)-6X calculation 0 1 H H Link1-- %chk=h2.chk # Geom=AllCheck Guess=Read BMK/6-31G(2df,p) Freq --Link1-- %chk=h2.chk # Geom=AllCheck Guess=Read CCSD(T,FrzG4)/GTBas1 --Link1-- %chk=h2.chk # Geom=AllCheck Guess=Read MP2(FrzG4)/GTMP2LargeXP --Link1-- %chk=h2.chk # Geom=AllCheck Guess=Read HF/GFHFB3 --Link1-- %chk=h2.chk # Geom=AllCheck Guess=Read HF/GFHFB4 S2

3 Table S1. Reactions in the DBH24, RR49 and PR8 Sets. DBH24-1 H N 2 O OH N 2 DBH24-2 H ClH HCl H DBH24-3 CH 3 FCl CH 3 F Cl DBH24-4 ClCH 3 Cl ClCH3Cl DBH24-5 FCH 3 Cl FCH 3 Cl DBH24 DBH24-6 OH CH 3 F HOCH 3 F DBH24-7 H N 2 HN 2 DBH24-8 H C 2 H 4 C 2 H 5 DBH24-9 HCN HNC DBH24-10 OH CH 4 CH 3 H 2 O DBH24-11 H OH O H 2 DBH24-12 H H 2 S H 2 HS ADD1 ADD2 ADD3 ADD4 ADD5 ADD6 ADD7 ADD8 ADD9 ADD10 RR49 Me CH 2 =CH 2 Me CH 2 CH 2 Et CH 2 =CH 2 Et CH 2 CH 2 i-pr CH 2 =CH 2 i-pr CH 2 CH 2 Me S=CH 2 Me SCH 2 Et S=CH 2 Et SCH 2 i-pr S=CH 2 i-pr SCH 2 Me O=CH 2 Me OCH 2 Et O=CH 2 Et OCH 2 i-pr O=CH 2 i-pr OCH 2 Me CH 2 =CHMe Me CH 2 C HMe ADD11 Me CH 2 =CMe 2 Me CH 2 C Me 2 ADD12 Me S=CHMe Me SC HMe ADD13 Me S=CMe 2 Me SC Me 2 ADD14 Me O=CHMe Me OC HMe ADD15 Me O=CMe 2 Me OC Me 2 ADD16 ADD17 ADD18 Me CH 2 =CHCN Me CH 2 C HCN Me CH 2 =CHF Me CH 2 C HF Me CH 2 =CHOMe Me CH 2 C HOMe ADD19 Me CH 2 =CHNH 2 Me CH 2 C HNH 2 ADD20 Me CH 2 =CHCHO Me CH 2 C HCHO ADD21 Me CH 2 =CF 2 Me CH 2 C F 2 ABS1 ABS2 ABS3 ABS4 ABS5 Me CH 2 CH 2 CH 4 Me CH 2 CH 3 CH 3 Et CH 2 CH 2 CH 4 Et CH 2 CH 3 CH 3 i-pr CH 2 CH 2 CH 4 i-pr CH 2 CH 3 CH 3 Me SCH 2 CH 4 Me SCH 3 CH 3 Et SCH 2 CH 4 Et SCH 3 CH 3 S3

4 ABS6 ABS7 ABS8 ABS9 ABS10 ABS11 ABS12 ABS13 ABS14 ABS15 ABS16 ABS17 ABS18 ABS19 ABS20 ABS21 ABS22 ABS23 ABS24 ABS25 ABS26 ABS27 ABS28 PR8-1 PR8-2 PR8-3 PR8-4 PR8-5 PR8-6 PR8-7 PR8-8 i-pr SCH 2 CH 4 i-pr SCH 3 CH 3 Me OCH 2 CH 4 Me OCH 3 CH 3 Et OCH 2 CH 4 Et OCH 3 CH 3 i-pr OCH 2 CH 4 i-pr OCH 3 CH 3 Me CH 2 C HMe CH 4 Et CH 2 CH 3 CH 3 Me CH 2 C Me 2 CH 4 i-pr CH 2 CH 3 CH 3 Me SC HMe CH 4 Et SCH 3 CH 3 Me SC Me 2 CH 4 i-pr SCH 3 CH 3 Me OC HMe CH 4 Et OCH 3 CH 3 Me OC Me 2 CH 4 i-pr OCH 3 CH 3 Me CH 2 C HCN CH 4 Me CH 2 CH 2 CN CH 3 Me CH 2 C HF CH 4 Me CH 2 CH 2 F CH 3 Me CH 2 C HOMe CH 4 Me CH 2 CH 2 OMe CH 3 Me CH 2 C HNH 2 CH 4 Me CH 2 CH 2 NH 2 CH 3 Me CH 2 C HCHO CH 4 Me CH 2 CH 2 CHO CH 3 Me CH 2 C F 2 CH 4 Me CH 2 CHF 2 CH 3 Et CH 4 EtH CH 3 i-pr CH 4 PrH CH 3 t-bu CH 4 t-buh CH 3 F 3 C CH 4 F 3 CH CH 3 Cl 3 C CH 4 Cl 3 CH CH 3 MeO 2 CCH 2 CH 4 MeO 2 CCH 3 CH 3 NCC Me 2 CH 4 NCCHMe 2 CH 3 PR8 Cyclobutene 1,3-Butadiene cis-1,3,5-hexatriene 1,3-Cyclohexadiene o-xylylene Benzocyclobutane 1,3-Pentadiene 1,3-Pentadiene 1,3-Cyclopentadiene 1,3-Cyclopentadiene 1,5-Hexadiene 1,5-Hexadiene 1,3-Butadiene Ethylene Cyclohexene 1,3-Cyclopentadiene Ethylene Norbornene S4

5 Table S2. Zero-Point Vibrational Energies and Thermal Corrections (kj mol 1 ), and G4(MP2)-6X Total Electronic Energies (hartrees). Species ZPVE ΔH 298 G4(MP2)-6X atoms H ( 2 S) He ( 1 S) Li ( 2 S) Be ( 1 S) B ( 2 P) C ( 3 P) N ( 4 S) O ( 3 P) F ( 2 P) Ne ( 1 S) Na ( 2 S) Mg ( 1 S) Al ( 2 P) Si ( 3 P) P ( 4 S) S ( 3 P) Cl ( 2 P) Ar ( 1 S) K ( 2 S) Ca ( 1 S) Ga ( 2 P) Ge ( 3 P) As ( 4 S) Se ( 3 P) Br ( 2 P) Kr ( 1 S) atomic cations He ( 2 S) Li ( 1 S) Be ( 2 S) B ( 1 S) C ( 2 P) N ( 3 P) O ( 4 S) F ( 3 P) Ne ( 2 P) Na ( 1 S) Mg ( 2 S) S5

6 Al ( 1 S) Si ( 2 P) P ( 3 P) S ( 4 S) Cl ( 3 P) Ar ( 2 P) atomic anions Li ( 1 S) B ( 3 P) C ( 4 S) O ( 2 P) F ( 1 S) Na ( 1 S) Al ( 3 P) Si ( 4 S) P ( 3 P) S ( 2 P) Cl ( 1 S) W4/08 B 2 H BHF BF C 2 H H 2 CN NCCN CH 2 NH CH 3 NH CH 3 NH CF N 2 H N 2 H N 2 H FO F 2 O AlF Si 2 H P SO SO OCS CS S 2 O S S6

7 S BeCl CCl AlCl ClCN OClO ClOO Cl 2 O H OH HF H 2 O CH CH CH CH C 2 H C 2 H NH C N CO CN NO O OF F PH HS H 2 S HCl SO ClO ClF P S Cl Be B BH BH BN (singlet) BF NH NH S7

8 HCN HOF AlH AlH AlF AlCl SiH SiH SiO SiF CS BN (triplet) CF BeF CH 2 C CH 2 CH C 2 H CH 2 NH HCO H 2 CO CO HNO NO N 2 O O HO H 2 O F 2 O HOCl S 2 H DBH24 H N 2 O HCl CH FCl ClCH 3 Cl FCH 3 Cl OH CH 3 F N C 2 H HCN OH CH H 2 S S8

9 Cl FCH 3 Cl CH 3 OH F HN CH 3 CH HNC H 2 O O H HS DBH24-1 TS DBH24-2 TS DBH24-3 TS DBH24-4 TS DBH24-5 TS DBH24-6 TS DBH24-7 TS DBH24-8 TS DBH24-9 TS DBH24-10 TS DBH24-11 TS DBH24-12 TS HB16 HCl NH CO HF H 2 O HCN H 3 O NH HCC CN OH ClHNH COHF FHNH H 2 OH 2 O HClHCl HFH 2 O HFHF HFHCN NH 3 NH NH 3 H 2 O OCHF S9

10 H 3 OH 2 O NH 4 H 2 O HCCH 2 O CNH 2 O OHH 2 O WI9/04 He Ne Ar CH C 6 H C 2 H C 2 H HeNe HeAr NeNe NeAr CH 4 Ne C 6 H 6 Ne CH 4 CH C 2 H 2 C 2 H C 2 H 4 C 2 H G2/97' neutrals LiH BeH CH 2 ( 1 A 1 ) SiH 2 ( 1 A 1 ) SiH 2 ( 3 B 1 ) SiH PH Li LiF H 3 COH Na Si NaCl CH 3 Cl H 3 CSH BCl CF CCl COF SiF SiCl S10

11 ClNO NF PF ClF C 2 F C 2 Cl CF 3 CN CH 3 CCH (propyne) CH 2 =C=CH 2 (allene) C 3 H 4 (cyclopropene) CH 3 CH=CH 2 (propylene) C 3 H 6 (cyclopropane) C 3 H 8 (propane) CH 2 CHCHCH 2 (butadiene) C 4 H 6 (2-butyne) C 4 H 6 (methylene cyclopropane) C 4 H 6 (bicyclobutane) C 4 H 6 (cyclobutene) C 4 H 8 (cyclobutane) C 4 H 8 (isobutene) C 4 H 10 (trans butane) C 4 H 10 (isobutane) C 5 H 8 (spiropentane) C 6 H 6 (benzene) CH 2 F CHF CH 2 Cl CHCl CH 3 CN (methyl cyanide) CH 3 NO 2 (nitromethane) CH 3 ONO (methyl nitrite) CH 3 SiH 3 (methyl silane) HCOOH (formic acid) HCOOCH 3 (methyl formate) CH 3 CONH 2 (acetamide) C 2 H 4 NH (aziridine) (CH 3 ) 2 NH (dimethylamine) CH 3 CH 2 NH 2 (trans ethylamine) CH 2 CO (ketene) C 2 H 4 O (oxirane) CH 3 CHO (acetaldehyde) HCOCOH (glyoxal) CH 3 CH 2 OH (ethanol) S11

12 CH 3 OCH 3 (dimethylether) C 2 H 4 S (thiirane) (CH 3 ) 2 SO (dimethyl sulfoxide) C 2 H 5 SH (ethanethiol) CH 3 SCH 3 (dimethyl sulfide) CH 2 =CHF (vinyl fluoride) C 2 H 5 Cl (ethyl chloride) CH 2 =CHCl (vinyl chloride) CH 2 =CHCN (acrylonitrile) CH 3 COCH 3 (acetone) CH 3 COOH (acetic acid) CH 3 COF (acetyl fluoride) CH 3 COCl (acetyl chloride) CH 3 CH 2 CH 2 Cl (propyl chloride) (CH 3 ) 2 CHOH (isopropanol) C 2 H 5 OCH 3 (methyl ethyl ether) (CH 3 ) 3 N (trimethylamine) C 4 H 4 O (furan) C 4 H 4 S (thiophene) C 4 H 5 N (pyrrole) C 5 H 5 N (pyridine) C 2 H 3 ( 2 A') CH 3 CO ( 2 A') H 2 COH ( 2 A) CH 3 O CS ( 2 A') CH 3 CH 2 O ( 2 A'') CH 3 S ( 2 A') C 2 H 5 ( 2 A') (CH 3 ) 2 CH ( 2 A') (CH 3 ) 3 C (t-butyl radical) PO PH SiH B 2 F CF C 6 H 5 CH 3 (toluene) CH 3 F CH 2 S CH 2 SH CH 3 OF C 6 H 5 OH (phenol) C 6 H 5 NH 2 (aniline) B 2 H S12

13 N 2 H N 2 H HOF Si 2 H Si 2 H Si 2 H C 2 (singlet) C 2 O (triplet CCO) NCO (doublet) OF (doublet) S 2 O H 2 C=C=C ( 1 A 1 ) H 2 C=C=CH CH 2 CHCH HCF ( 1 A') CH 2 CN CH 2 NC CHCO CH 2 CHO CH 3 CH 2 S HNO HO 2 ( 2 A" HOO) G2/97 cations CH 4 NH OH OH FH SiH PH PH 2 PH SH SH 2 ( 2 B 1 ) SH 2 ( 2 A 1 ) ClH C 2 H 2 C 2 H CO N 2 ( 2 Σ) N 2 ( 2 Π) O S13

14 P 2 ( 2 Π) S 2 Cl ClF CS BF 3 BCl 3 B 2 F 4 CO 2 CF COS CS 2 CH 2 CH 3 C 2 H C 3 H 4 (cyclopropene ) CH 2 =C=CH sec-c 3 H C 6 H C 6 H 5 CH CN CHO CH 2 OH CH 3 O CH 3 OH CH 3 F CH 2 S HSCH CH 3 SH CH 3 Cl C 2 H 5 OH CH 3 CHO CH 3 OF C 2 H 4 S (thiirane ) NCCN C 4 H 4 O (furan ) C 4 H 5 N (pyrrole ) C 6 H 5 OH C 6 H 5 NH B 2 H S14

15 NH NH 2 N 2 H 2 N 2 H HOF SiH SiH Si 2 H Si 2 H Si 2 H Si 2 H G2/97 anions CH CH 2 CH NH NH OH SiH SiH SiH PH PH SH O NO CN PO S 2 Cl CC (doublet) C 2 O (doublet CCO ) CF 2 ( 2 B 1 ) NCO (singlet) NO 2 (singlet ONO ) O OF (singlet) SO S 2 O C 2 H C 2 H S15

16 H 2 C=C=C H 2 C=C=CH CH 2 CHCH HCO HCF ( 2 A") CH 3 O CH 3 S CH 2 S CH 2 CN CH 2 NC CHCO CH 2 CHO CH 3 CO CH 3 CH 2 O CH 3 CH 2 S LiH HNO HO 2 ( 1 A' HOO ) protonated species NH 4 OH 3 C 2 H 3 SiH 5 PH 4 SH 3 ClH 2 H 3 G3/99' neutrals C 4 H 6 (methyl allene) C 5 H 8 (isoprene) C 5 H 10 (cyclopentane) C 5 H 12 (n-pentane) C 5 H 12 (neopentane) C 6 H 8 (1,3-cyclohexadiene) C 6 H 8 (1,4-cyclohexadiene) C 6 H 12 (cyclohexane) C 6 H 14 (n-hexane) C 6 H 14 (3-methyl pentane) C 6 H 5 CH 3 (toluene) C 7 H 16 (n-heptane) C 8 H 8 (cyclooctatetraene) C 8 H 18 (n-octane) S16

17 C 10 H 8 (naphthalene) C 10 H 8 (azulene) CH 3 COOCH 3 (acetic acid methyl ester) (CH 3 ) 3 COH (t-butanol) C 6 H 5 NH 2 (aniline) C 6 H 5 OH (phenol) C 4 H 6 O (divinyl ether) C 4 H 8 O (tetrahydrofuran) C 5 H 8 O (cyclopentanone) C 6 H 4 O 2 (benzoquinone) C 4 H 4 N 2 (pyrimidine) C 2 H 6 O 2 S (dimethyl sulphone) C 6 H 5 Cl (chlorobenzene) N=C-CH 2 -CH 2 -C=N (butanedinitrile) C 4 H 4 N 2 (1,4-dipyridine) (pyrazine) CH 3 -C(=O)-CCH CH 3 -CH=CH-CHO (crotonaldehyde) CH 3 -C(=O)-O-C(=O)-CH 3 (acetic anhydride) C 4 H 6 S (2,5-dihydrothiophene) (CH 3 ) 2 CH-CN CH 3 -CO-CH 2 -CH 3 (methyl ethyl ketone) (CH 3 ) 2 CH-CHO C 4 H 8 O 2 (cyc-ch2-ch2-o-ch2-ch2-o (para)) (1,4-dioxane) C 4 H 8 S (tetrahydrothiophene) (CH 3 ) 3 C-Cl (t-butyl chloride) CH 3 -CH 2 -CH 2 -CH 2 -Cl (n-butyl chloride) C 4 H 8 NH (tetrahydropyrrole) CH 3 -CH 2 -CH(CH 3 )-NO 2 (2-nitrobutane) CH 3 -CH 2 -O-CH 2 -CH 3 (diethyl ether) CH 3 -CH(OCH 3 ) 2 (acetaldehyde dimethyl acetal) (CH 3 ) 3 C-SH (t-butanethiol) CH 3 -CH 2 -S-S-CH 2 -CH 3 (diethyl disulfide) (CH 3 ) 3 C-NH 2 (t-butylamine) Si(CH 3 ) 4 (tetramethylsilane) C 5 H 6 S cyc-ch=ch-s-c(ch 3 )=CH- (2-methyl thiophene) cyc-ch=ch-n(ch 3 )-CH=CH- (N-methyl pyrrole) C 5 H 10 O (tetrahydropyran) CH 3 -CH 2 -CO-CH 2 -CH 3 (diethyl ketone) C 5 H 10 O 2 CH 3 -C(=O)-O-CH(CH 3 ) 2 (Isopropyl acetate) C 5 H 10 S (tetrahydrothiopyran) cyc-c 5 H 10 NH (piperidine) S17

18 (CH 3 ) 3 C-O-CH 3 (t-butyl methyl ether) C 6 H 4 F 2 (1,3-difluorobenzene) C 6 H 4 F 2 (1,4-difluorobenzene) C 6 H 5 F (fluorobenzene) (CH 3 ) 2 CH-O-CH(CH 3 ) 2 (di-isopropyl ether) PF SF SCl POCl PCl Cl 2 O 2 S PCl Cl 2 S SiCl CF 3 Cl C 2 F CF C 6 H 5 (phenyl radical) RR49 Me Et i-pr CH 2 =CH Me CH 2 CH 2 Et CH 2 CH 2 i-pr CH 2 CH S=CH Me SCH 2 Et SCH 2 i-pr SCH O=CH Me OCH 2 Et OCH 2 i-pr OCH CH 2 =CHMe Me CH 2 C HMe CH 2 =CMe Me CH 2 C Me S=CHMe Me SC HMe S=CMe Me SC Me S18

19 O=CHMe Me OC HMe O=CMe Me OC Me CH 2 =CHCN Me CH 2 C HCN CH 2 =CHF Me CH 2 C HF CH 2 =CHOMe Me CH 2 C HOMe CH 2 =CHNH Me CH 2 C HNH CH 2 =CHCHO Me CH 2 C HCHO CH 2 =CF Me CH 2 C F CH Me CH 2 CH Et CH 2 CH i-pr CH 2 CH Me SCH Et SCH i-pr SCH Me OCH Et OCH i-pr OCH Me CH 2 CH 2 CN Me CH 2 CH 2 F Me CH 2 CH 2 OMe Me CH 2 CH 2 NH Me CH 2 CH 2 CHO Me CH 2 CHF EtH t-bu t-buh F 3 C F 3 CH Cl 3 C Cl 3 CH MeO 2 CCH MeO 2 CCH NCC Me S19

20 NCCHMe PR8 Cyclobutene cis-1,3,5-hexatriene o-xylylene ,3-Pentadiene ,3-Cyclopentadiene ,5-Hexadiene ,3-Butadiene Ethylene ,3-Cyclohexadiene Benzocyclobutane Cyclohexene Norbornene PR8-1 TS PR8-2 TS PR8-3 TS PR8-4 TS PR8-5 TS PR8-6 TS PR8-7 TS PR8-8 TS Table S3. Deviations (kj mol 1 ) from Experimental and W1 Values. Property W4/08 AE Deviation B 2 H BHF BF C 2 H H 2 CN 0.50 NCCN CH 2 NH CH 3 NH CH 3 NH CF N 2 H N 2 H N 2 H FO F 2 O AlF Si 2 H P S20

21 SO SO OCS 1.79 CS S 2 O S S BeCl CCl AlCl ClCN 0.83 OClO ClOO Cl 2 O 0.01 H OH 0.48 HF 0.53 H 2 O CH 1.28 CH CH CH C 2 H C 2 H NH C N CO 1.37 CN NO 0.95 O OF 0.03 F PH HS H 2 S HCl SO 0.93 ClO ClF 0.27 P S Cl Be B S21

22 BH 1.12 BH BN (singlet) 1.96 BF 0.32 NH 0.95 NH HCN HOF AlH 1.02 AlH AlF 0.90 AlCl 0.54 SiH 0.76 SiH SiO 0.29 SiF 0.93 CS 2.52 BN (triplet) CF 1.28 BeF CH 2 C 0.34 CH 2 CH 0.72 C 2 H CH 2 NH 0.18 HCO 1.08 H 2 CO 0.79 CO HNO 0.72 NO N 2 O 0.23 O HO H 2 O F 2 O HOCl S 2 H DBH24 ΔH DBH24-1 fwd DBH24-2 fwd 0.80 DBH24-3 fwd DBH24-4 fwd 0.61 DBH24-5 fwd 0.78 DBH24-6 fwd 1.38 DBH24-7 fwd DBH24-8 fwd DBH24-9 fwd DBH24-10 fwd 1.48 S22

23 DBH24-11 fwd 0.22 DBH24-12 fwd DBH24-1 rev 0.23 DBH24-2 rev 0.80 DBH24-3 rev DBH24-4 rev 0.61 DBH24-5 rev 0.12 DBH24-6 rev 1.44 DBH24-7 rev DBH24-8 rev DBH24-9 rev DBH24-10 rev 1.23 DBH24-11 rev 1.09 DBH24-12 rev 1.74 HB16 HB ClHNH COHF 0.18 FHNH H 2 OH 2 O HClHCl HFH 2 O HFHF HFHCN NH 3 NH NH 3 H 2 O OCHF H 3 OH 2 O NH 4 H 2 O HCCH 2 O CNH 2 O OHH 2 O WI9/04 BE HeNe HeAr NeNe NeAr CH 4 Ne C 6 H 6 Ne CH 4 CH C 2 H 2 C 2 H C 2 H 4 C 2 H G2/97' ΔH f LiH BeH CH 2 ( 1 A 1 ) SiH 2 ( 1 A 1 ) S23

24 SiH 2 ( 3 B 1 ) SiH PH Li LiF H 3 COH Na Si NaCl 0.53 CH 3 Cl H 3 CSH BCl CF CCl COF SiF SiCl ClNO 0.71 NF PF ClF C 2 F C 2 Cl CF 3 CN CH 3 CCH (propyne) 0.40 CH 2 =C=CH 2 (allene) C 3 H 4 (cyclopropene) 1.51 CH 3 CH=CH 2 (propylene) C 3 H 6 (cyclopropane) 0.44 C 3 H 8 (propane) CH 2 CHCHCH 2 (butadiene) C 4 H 6 (2-butyne) 0.95 C 4 H 6 (methylene cyclopropane) C 4 H 6 (bicyclobutane) 1.79 C 4 H 6 (cyclobutene) 1.20 C 4 H 8 (cyclobutane) C 4 H 8 (isobutene) C 4 H 10 (trans butane) C 4 H 10 (isobutane) 0.08 C 5 H 8 (spiropentane) 0.04 C 6 H 6 (benzene) CH 2 F CHF S24

25 CH 2 Cl CHCl CH 3 CN (methyl cyanide) 0.04 CH 3 NO 2 (nitromethane) 0.00 CH 3 ONO (methyl nitrite) 0.05 CH 3 SiH 3 (methyl silane) 0.55 HCOOH (formic acid) 0.19 HCOOCH 3 (methyl formate) CH 3 CONH 2 (acetamide) 1.97 C 2 H 4 NH (aziridine) 0.39 (CH 3 ) 2 NH (dimethylamine) 0.64 CH 3 CH 2 NH 2 (trans ethylamine) 0.02 CH 2 CO (ketene) C 2 H 4 O (oxirane) CH 3 CHO (acetaldehyde) HCOCOH (glyoxal) CH 3 CH 2 OH (ethanol) 0.27 CH 3 OCH 3 (dimethylether) C 2 H 4 S (thiirane) (CH 3 ) 2 SO (dimethyl sulfoxide) 0.03 C 2 H 5 SH (ethanethiol) CH 3 SCH 3 (dimethyl sulfide) CH 2 =CHF (vinyl fluoride) C 2 H 5 Cl (ethyl chloride) 0.24 CH 2 =CHCl (vinyl chloride) CH 2 =CHCN (acrylonitrile) 1.69 CH 3 COCH 3 (acetone) 0.34 CH 3 COOH (acetic acid) 1.17 CH 3 COF (acetyl fluoride) 0.92 CH 3 COCl (acetyl chloride) 0.45 CH 3 CH 2 CH 2 Cl (propyl chloride) (CH 3 ) 2 CHOH (isopropanol) 0.24 C 2 H 5 OCH 3 (methyl ethyl ether) (CH 3 ) 3 N (trimethylamine) C 4 H 4 O (furan) 0.44 C 4 H 4 S (thiophene) C 4 H 5 N (pyrrole) 0.24 C 5 H 5 N (pyridine) C 2 H 3 ( 2 A') CH 3 CO ( 2 A') H 2 COH ( 2 A) 0.08 CH 3 O CS ( 2 A') 0.41 CH 3 CH 2 O ( 2 A'') 0.20 S25

26 CH 3 S ( 2 A') 0.01 C 2 H 5 ( 2 A') 0.04 (CH 3 ) 2 CH ( 2 A') (CH 3 ) 3 C (t-butyl radical) 0.00 G2/97 IE H 1.49 He 0.49 Li 0.42 Be 1.07 B C N O F 0.04 Ne 0.56 Na 0.00 Mg Al 0.04 Si P S Cl Ar CH NH OH OH FH 0.20 SiH PH PH PH SH SH 2 ( 2 B 1 ) SH 2 ( 2 A 1 ) ClH C 2 H C 2 H CO 0.64 N 2 ( 2 Σ) N 2 ( 2 Π) O P 2 ( 2 Π) S Cl ClF S26

27 CS 1.60 BF BCl B 2 F CO CF COS CS CH CH C 2 H cyclopropene CH 2 =C=CH sec-c 3 H C 6 H C 6 H 5 CH CN CHO 0.85 CH 2 OH 0.04 CH 3 O CH 3 OH 0.96 CH 3 F 2.87 CH 2 S 0.01 HSCH CH 3 SH 0.07 CH 3 Cl 1.03 C 2 H 5 OH CH 3 CHO 0.24 CH 3 OF 0.20 thiirane 0.18 NCCN 1.30 furan 1.70 pyrrole 0.93 C 6 H 5 OH 1.83 C 6 H 5 NH B 2 H NH NH N 2 H N 2 H HOF SiH SiH Si 2 H S27

28 Si 2 H Si 2 H Si 2 H G2/97 EA Li 2.97 B C O F 2.22 Na 1.95 Al Si P S Cl CH CH CH NH NH OH 0.94 SiH SiH SiH PH PH SH O NO CN 1.52 PO S Cl CC CCO 0.22 CF 2 ( 2 B 1 ) NCO ONO 0.18 O OF SO S 2 O 1.72 C 2 H 2.21 C 2 H H 2 C=C=C 1.64 H 2 C=C=CH 1.78 S28

29 CH 2 CHCH HCO 0.59 HCF ( 2 A") CH 3 O 1.52 CH 3 S 1.03 CH 2 S CH 2 CN 0.61 CH 2 NC 2.96 CHCO CH 2 CHO 0.25 CH 3 CO 0.78 CH 3 CH 2 O 0.91 CH 3 CH 2 S 0.03 LiH 1.64 HNO HOO ( 1 A') G2/97 PA NH OH C 2 H SiH PH SH ClH 0.30 H G3/99' ΔH f methyl allene isoprene cyclopentane n-pentane neo pentane ,3-cyclohexadiene ,4-cyclohexadiene 0.61 cyclohexane 0.21 n-hexane methyl pentane toluene n-heptane cyclooctatetraene 0.00 n-octane naphthalene azulene 0.00 acetic acid methyl ester 0.94 t-butanol 0.03 aniline 0.21 phenol 0.98 S29

30 divinyl ether 0.88 tetrahydrofuran 0.51 cyclopentanone benzoquinone 2.15 pyrimidine dimethyl sulphone 0.38 chlorobenzene butanedinitrile ,4-dipyridine pyrazine 1.97 CH 3 -C(=O)-CCH 3.21 crotonaldehyde acetic anhydride ,5-dihydrothiophene (CH 3 ) 2 CH-CN 1.70 methyl ethyl ketone 0.50 (CH 3 ) 2 CH-CHO ,4-dioxane 0.18 tetrahydrothiophene t-butyl chloride n-butyl chloride 0.05 tetrahydropyrrole nitrobutane diethyl ether acetaldehyde dimethyl acetal t-butanethiol diethyl disulfide 0.00 t-butylamine 0.16 tetramethylsilane methyl thiophene N-methyl pyrrole tetrahydropyran 0.37 diethyl ketone isopropyl acetate 0.47 tetrahydrothiopyran piperidine 0.66 t-butyl methyl ether ,3-difluorobenzene ,4-difluorobenzene 0.83 fluorobenzene 0.45 di-isopropyl ether PF SF SCl POCl PCl Cl 2 O 2 S 1.99 PCl Cl 2 S S30

31 SiCl CF 3 Cl C 2 F CF phenyl radical 0.31 RR49 ΔH r ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ADD ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS ABS S31

32 ABS ABS ABS ABS ABS ABS PR8 ΔH PR PR PR PR PR PR PR PR S32