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

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

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 0.000000 0.000000 0.371049 H 0.000000 0.000000-0.371049 --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

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

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

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) 0.00 6.20-0.50238 He ( 1 S) 0.00 6.20-2.90687 Li ( 2 S) 0.00 6.20-7.43513 Be ( 1 S) 0.00 6.20-14.62403 B ( 2 P) 0.00 6.20-24.61077 C ( 3 P) 0.00 6.20-37.79602 N ( 4 S) 0.00 6.20-54.53555 O ( 3 P) 0.00 6.20-75.00628 F ( 2 P) 0.00 6.20-99.66427 Ne ( 1 S) 0.00 6.20-128.85838 Na ( 2 S) 0.00 6.20-162.00381 Mg ( 1 S) 0.00 6.20-199.78432 Al ( 2 P) 0.00 6.20-241.94500 Si ( 3 P) 0.00 6.20-288.94915 P ( 4 S) 0.00 6.20-340.83893 S ( 3 P) 0.00 6.20-397.67946 Cl ( 2 P) 0.00 6.20-459.70708 Ar ( 1 S) 0.00 6.20-527.08640 K ( 2 S) 0.00 6.20-599.41798 Ca ( 1 S) 0.00 6.20-677.06170 Ga ( 2 P) 0.00 6.20-1923.60843 Ge ( 3 P) 0.00 6.20-2075.70775 As ( 4 S) 0.00 6.20-2234.58604 Se ( 3 P) 0.00 6.20-2400.25126 Br ( 2 P) 0.00 6.20-2572.85743 Kr ( 1 S) 0.00 6.20-2752.49346 atomic cations He ( 2 S) 0.00 6.20-2.00243 Li ( 1 S) 0.00 6.20-7.23639 Be ( 2 S) 0.00 6.20-14.27983 B ( 1 S) 0.00 6.20-24.30849 C ( 2 P) 0.00 6.20-37.38505 N ( 3 P) 0.00 6.20-54.00317 O ( 4 S) 0.00 6.20-74.50673 F ( 3 P) 0.00 6.20-99.02403 Ne ( 2 P) 0.00 6.20-128.06518 Na ( 1 S) 0.00 6.20-161.81495 Mg ( 2 S) 0.00 6.20-199.50372 S5

Al ( 1 S) 0.00 6.20-241.72503 Si ( 2 P) 0.00 6.20-288.65146 P ( 3 P) 0.00 6.20-340.45610 S ( 4 S) 0.00 6.20-397.30323 Cl ( 3 P) 0.00 6.20-459.23358 Ar ( 2 P) 0.00 6.20-526.50924 atomic anions Li ( 1 S) 0.00 6.20-7.46257 B ( 3 P) 0.00 6.20-24.61504 C ( 4 S) 0.00 6.20-37.83670 O ( 2 P) 0.00 6.20-75.05896 F ( 1 S) 0.00 6.20-99.79276 Na ( 1 S) 0.00 6.20-162.02705 Al ( 3 P) 0.00 6.20-241.95834 Si ( 4 S) 0.00 6.20-288.99622 P ( 3 P) 0.00 6.20-340.86186 S ( 2 P) 0.00 6.20-397.75392 Cl ( 1 S) 0.00 6.20-459.83951 W4/08 B 2 H 6 164.69 11.92-53.19691 BHF 2 47.19 10.72-225.09187 BF 3 32.82 11.72-324.34813 C 2 H 6 192.94 11.64-79.74094 H 2 CN 65.63 10.19-93.88475 NCCN 43.51 12.28-185.46220 CH 2 NH 2 129.98 11.62-95.10808 CH 3 NH 126.86 11.55-95.09677 CH 3 NH 2 165.92 11.59-95.76980 CF 2 18.82 10.32-237.53679 N 2 H 35.41 9.99-109.93152 N 2 H 2 74.46 9.99-110.54855 N 2 H 4 139.83 11.08-111.77702 FO 2 16.11 10.90-249.88797 F 2 O 2 24.72 12.74-349.57829 AlF 3 20.20 14.34-541.62150 Si 2 H 6 133.77 15.75-581.76232 P 4 15.16 14.73-1363.81079 SO 2 18.67 10.53-548.10315 SO 3 33.24 11.71-623.24388 OCS 24.38 9.94-511.01764 CS 2 18.34 10.55-833.60387 S 2 O 13.62 11.18-870.69286 S 3 9.24 11.97-1193.30160 S6

S 4 14.79 15.40-1591.08332 BeCl 2 12.16 12.16-934.39193 CCl 2 11.08 11.45-957.49156 AlCl 3 12.63 16.55-1621.55713 ClCN 23.02 10.66-552.49304 OClO 14.83 10.82-609.91970 ClOO 13.10 11.62-609.91146 Cl 2 O 10.48 11.60-994.57891 H 2 26.28 8.68-1.18178 OH 22.34 8.68-75.68010 HF 24.51 8.68-100.39241 H 2 O 56.22 9.93-76.38151 CH 16.55 8.68-38.43423 CH 2 44.55 10.00-39.10489 CH 3 76.81 10.50-39.79360 CH 4 115.64 10.03-40.47483 C 2 H 42.85 9.00-76.51865 C 2 H 2 70.27 9.79-77.24214 NH 3 89.37 10.04-56.51631 C 2 9.31 8.69-75.82642 N 2 14.06 8.68-109.43546 CO 13.49 8.68-113.21782 CN 12.76 8.68-92.62036 NO 11.75 8.68-129.78654 O 2 10.30 8.68-150.20579 OF 7.08 8.73-174.75483 F 2 6.44 8.75-199.38892 PH 3 64.39 10.13-342.73017 HS 15.81 8.68-398.32085 H 2 S 39.06 9.97-398.97499 HCl 17.70 8.68-460.37850 SO 7.10 8.73-472.88706 ClO 5.02 8.86-534.81416 ClF 4.74 8.90-559.46964 P 2 4.41 8.95-681.86461 S 2 4.29 8.96-795.52331 Cl 2 3.64 9.10-919.50581 Be 2 1.38 10.04-29.25475 B 2 5.57 8.81-49.32694 BH 14.00 8.68-25.25013 BH 3 68.99 10.06-26.56351 BN (singlet) 10.48 8.68-79.31697 BF 8.27 8.70-124.56549 NH 19.88 8.68-55.17186 NH 2 49.93 9.93-55.83118 S7

HCN 42.50 9.18-93.33328 HOF 37.29 10.02-175.42384 AlH 10.76 8.68-242.56598 AlH 3 44.48 10.67-243.79139 AlF 4.70 8.90-341.87028 AlCl 2.82 9.34-701.84628 SiH 11.51 8.68-289.56971 SiH 4 84.65 10.58-291.47504 SiO 7.31 8.72-364.26205 SiF 4.75 8.90-388.84081 CS 7.59 8.71-435.75265 BN (triplet) 9.67 8.69-79.31455 CF 7.92 8.71-137.67308 BeF 2 18.47 10.86-214.44156 CH 2 C 60.88 11.23-77.17049 CH 2 CH 94.24 10.68-77.81044 C 2 H 4 131.44 10.53-78.49999 CH 2 NH 103.79 10.18-94.53895 HCO 34.21 9.99-113.75076 H 2 CO 69.43 10.02-114.40450 CO 2 31.34 9.32-188.43001 HNO 37.29 9.93-130.37316 NO 2 22.96 10.21-204.91152 N 2 O 28.73 9.54-184.50850 O 3 20.78 10.22-225.25092 HO 2 37.98 9.97-150.79407 H 2 O 2 70.55 10.93-151.44439 F 2 O 15.41 10.69-274.48197 HOCl 34.87 10.19-535.47806 S 2 H 24.09 10.50-796.12039 DBH24 H 0.00 6.20-0.50238 N 2 O 28.73 9.54-184.50850 HCl 17.70 8.68-460.37850 CH 3 76.81 10.50-39.79360 FCl 4.74 8.90-559.46964 ClCH 3 Cl 101.37 15.80-959.49504 FCH 3 Cl 97.09 16.53-599.45458 OH 22.74 8.68-75.74900 CH 3 F 101.89 10.14-139.64053 N 2 14.06 8.68-109.43546 C 2 H 4 131.44 10.53-78.49999 HCN 42.50 9.18-93.33328 OH 22.34 8.68-75.68010 CH 4 115.64 10.03-40.47483 H 2 S 39.06 9.97-398.97499 S8

Cl 0.00 6.20-459.70574 FCH 3 Cl 104.14 15.52-599.49492 CH 3 OH 133.09 11.39-115.62890 F 0.00 6.20-99.79276 HN 2 35.41 9.99-109.93152 CH 3 CH 2 153.13 12.92-79.06539 HNC 42.14 9.63-93.30949 H 2 O 56.22 9.93-76.38151 O 0.00 6.20-75.00592 H 2 26.28 8.68-1.18178 HS 15.81 8.68-398.32085 DBH24-1 TS 30.51 11.41-184.98377 DBH24-2 TS 14.88 10.95-460.85177 DBH24-3 TS 86.79 16.61-599.25261 DBH24-4 TS 96.47 14.75-959.47270 DBH24-5 TS 97.46 14.10-599.44785 DBH24-6 TS 128.06 15.54-215.39123 DBH24-7 TS 16.77 10.25-109.91503 DBH24-8 TS 135.40 12.41-78.99981 DBH24-9 TS 28.61 9.92-93.25840 DBH24-10 TS 131.56 14.66-116.14246 DBH24-11 TS 18.67 9.28-76.16497 DBH24-12 TS 37.19 11.62-399.47157 HB16 HCl 17.70 8.68-460.37850 NH 3 89.37 10.04-56.51631 CO 13.49 8.68-113.21782 HF 24.51 8.68-100.39241 H 2 O 56.22 9.93-76.38151 HCN 42.50 9.18-93.33328 H 3 O 89.23 10.19-76.65527 NH 4 128.27 9.98-56.85470 HCC 38.40 9.47-76.62964 CN 12.75 8.68-92.76464 OH 22.74 8.68-75.74900 ClHNH 3 115.06 14.79-516.90609 COHF 42.21 17.26-213.61322 FHNH 3 126.44 13.80-156.92773 H 2 OH 2 O 120.87 18.01-152.77062 HClHCl 41.06 15.29-920.75990 HFH 2 O 91.38 14.43-176.78743 HFHF 56.48 14.14-200.79169 HFHCN 74.96 15.47-193.73734 NH 3 NH 3 185.54 19.74-113.03732 NH 3 H 2 O 154.82 18.03-132.90766 OCHF 44.15 15.96-213.61569 S9

H 3 OH 2 O 147.58 15.45-153.08902 NH 4 H 2 O 192.15 17.55-133.26810 HCCH 2 O 100.31 17.07-153.03886 CNH 2 O 76.02 16.03-169.16993 OHH 2 O 82.47 13.73-152.17127 WI9/04 He 0.00 6.20-2.90687 Ne 0.00 6.20-128.85838 Ar 0.00 6.20-527.08640 CH 4 115.64 10.03-40.47483 C 6 H 6 259.47 14.30-231.97062 C 2 H 2 70.27 9.79-77.24214 C 2 H 4 131.44 10.53-78.49999 HeNe 0.29 10.88-131.76494 HeAr 0.14 11.02-529.99295 NeNe 0.12 11.04-257.71624 NeAr 0.16 11.00-655.94431 CH 4 Ne 116.87 16.14-169.33303 C 6 H 6 Ne 259.49 21.49-360.82886 CH 4 CH 4 232.15 16.13-80.94972 C 2 H 2 C 2 H 2 142.63 20.28-154.48660 C 2 H 4 C 2 H 4 267.86 19.66-157.00212 G2/97' neutrals LiH 8.60 8.69-8.03036 BeH 12.66 8.68-15.20791 CH 2 ( 1 A 1 ) 42.78 9.94-39.09067 SiH 2 ( 1 A 1 ) 29.07 10.01-290.19943 SiH 2 ( 3 B 1 ) 32.97 10.08-290.16540 SiH 3 58.32 10.43-290.81921 PH 2 36.47 9.97-342.08884 Li 2 1.93 9.72-14.90611 LiF 5.91 8.78-107.31958 H 3 COH 133.08 11.39-115.62891 Na 2 0.98 10.31-324.03363 Si 2 3.12 9.24-578.01916 NaCl 2.01 9.68-621.86621 CH 3 Cl 97.68 10.43-499.63895 H 3 CSH 118.50 11.96-438.23995 BCl 3 20.39 14.08-1404.24445 CF 4 45.21 12.83-437.21261 CCl 4 25.71 17.35-1877.12362 COF 2 37.64 11.13-312.79909 SiF 4 33.81 15.47-688.52186 SiCl 4 19.21 19.72-2128.38904 S10

ClNO 16.91 11.24-589.55264 NF 3 28.41 11.73-353.85584 PF 3 20.63 13.35-640.41185 ClF 3 18.94 13.69-758.90022 C 2 F 4 57.46 16.24-475.18485 C 2 Cl 4 40.54 19.77-1915.16959 CF 3 CN 60.17 15.90-430.14052 CH 3 CCH (propyne) 143.77 12.93-116.52032 CH 2 =C=CH 2 (allene) 142.06 12.56-116.51932 C 3 H 4 (cyclopropene) 143.32 11.44-116.48275 CH 3 CH=CH 2 (propylene) 205.93 13.19-117.77387 C 3 H 6 (cyclopropane) 209.12 11.58-117.76094 C 3 H 8 (propane) 265.28 14.78-119.01080 CH 2 CHCHCH 2 (butadiene) 219.71 14.90-155.81203 C 4 H 6 (2-butyne) 217.72 17.45-155.79691 C 4 H 6 (methylene cyclopropane) 219.20 13.99-155.77982 C 4 H 6 (bicyclobutane) 221.40 12.77-155.76794 C 4 H 6 (cyclobutene) 223.34 12.77-155.79274 C 4 H 8 (cyclobutane) 285.02 13.50-157.03416 C 4 H 8 (isobutene) 277.26 16.84-157.04941 C 4 H 10 (trans butane) 340.72 17.77-158.28091 C 4 H 10 (isobutane) 339.96 17.47-158.28363 C 5 H 8 (spiropentane) 295.68 15.91-195.04494 C 6 H 6 (benzene) 259.47 14.30-231.97062 CH 2 F 2 85.47 10.70-238.82562 CHF 3 66.65 11.59-338.02111 CH 2 Cl 2 76.15 11.88-958.80382 CHCl 3 52.31 14.26-1417.96634 CH 3 CN (methyl cyanide) 117.51 12.05-132.61598 CH 3 NO 2 (nitromethane) 129.95 13.82-244.80925 CH 3 ONO (methyl nitrite) 127.17 13.76-244.80506 CH 3 SiH 3 (methyl silane) 161.31 13.55-330.75950 HCOOH (formic acid) 88.94 10.83-189.61178 HCOOCH 3 (methyl formate) 161.94 14.20-228.86636 CH 3 CONH 2 (acetamide) 191.11 16.04-209.02671 C 2 H 4 NH (aziridine) 181.06 11.20-133.78596 (CH 3 ) 2 NH (dimethylamine) 238.65 14.27-135.02990 CH 3 CH 2 NH 2 (trans ethylamine) 239.58 14.22-135.04222 CH 2 CO (ketene) 82.01 11.80-152.45167 C 2 H 4 O (oxirane) 148.19 10.90-153.64481 CH 3 CHO (acetaldehyde) 143.46 12.74-153.68673 HCOCOH (glyoxal) 96.99 13.66-227.62058 CH 3 CH 2 OH (ethanol) 206.76 14.01-154.90317 S11

CH 3 OCH 3 (dimethylether) 206.29 13.94-154.88422 C 2 H 4 S (thiirane) 141.70 11.54-476.27735 (CH 3 ) 2 SO (dimethyl sulfoxide) 204.96 17.50-552.65472 C 2 H 5 SH (ethanethiol) 192.16 15.04-477.51059 CH 3 SCH 3 (dimethyl sulfide) 194.06 15.80-477.50927 CH 2 =CHF (vinyl fluoride) 114.10 11.34-177.67626 C 2 H 5 Cl (ethyl chloride) 172.10 13.10-538.91202 CH 2 =CHCl (vinyl chloride) 110.22 11.86-537.67170 CH 2 =CHCN (acrylonitrile) 131.64 13.53-170.64563 CH 3 COCH 3 (acetone) 215.50 16.81-192.96714 CH 3 COOH (acetic acid) 161.74 14.10-228.89236 CH 3 COF (acetyl fluoride) 127.94 13.56-252.89370 CH 3 COCl (acetyl chloride) 122.83 14.66-612.87577 CH 3 CH 2 CH 2 Cl (propyl chloride) 245.36 16.78-578.18214 (CH 3 ) 2 CHOH (isopropanol) 279.38 17.01-194.17895 C 2 H 5 OCH 3 (methyl ethyl ether) 280.16 16.98-194.15881 (CH 3 ) 3 N (trimethylamine) 312.23 16.47-174.29489 C 4 H 4 O (furan) 181.63 12.33-229.78325 C 4 H 4 S (thiophene) 171.17 13.44-552.41038 C 4 H 5 N (pyrrole) 213.93 12.97-209.93925 C 5 H 5 N (pyridine) 229.34 13.97-248.00106 C 2 H 3 ( 2 A') 94.28 10.69-77.81043 CH 3 CO ( 2 A') 112.11 12.78-153.03310 H 2 COH ( 2 A) 97.49 11.22-114.96206 CH 3 O CS ( 2 A') 95.14 10.35-114.94727 CH 3 CH 2 O ( 2 A'') 167.13 13.82-154.22138 CH 3 S ( 2 A') 97.37 10.50-437.59165 C 2 H 5 ( 2 A') 153.13 12.91-79.06538 (CH 3 ) 2 CH ( 2 A') 226.35 16.50-118.33960 (CH 3 ) 3 C (t-butyl radical) 299.54 19.97-157.61556 PO 7.54 8.71-416.07532 PH 14.10 8.68-341.45872 SiH 11.53 8.68-289.56971 B 2 F 4 50.75 18.31-448.98273 CF 2 18.82 10.32-237.53679 C 6 H 5 CH 3 (toluene) 330.26 18.90-271.24457 CH 3 F 101.87 10.14-139.64053 CH 2 S 63.62 10.23-437.00115 CH 2 SH 80.98 12.91-437.57455 CH 3 OF 110.51 12.36-214.68658 C 6 H 5 OH (phenol) 270.79 17.31-307.14085 C 6 H 5 NH 2 (aniline) 302.59 18.13-287.28224 B 2 H 4 104.79 11.44-51.94517 S12

N 2 H 2 74.47 9.99-110.54855 N 2 H 3 103.43 10.88-111.13237 HOF 37.29 10.02-175.42384 Si 2 H 2 42.14 10.88-579.27288 Si 2 H 4 83.79 14.64-580.50249 Si 2 H 5 107.27 15.74-581.11158 C 2 (singlet) 8.41 8.70-75.83089 C 2 O (triplet CCO) 23.08 10.60-151.10242 NCO (doublet) 26.37 9.69-167.84499 OF (doublet) 7.08 8.73-174.75483 S 2 O 13.62 11.18-870.69286 H 2 C=C=C ( 1 A 1 ) 79.97 12.59-115.19117 H 2 C=C=CH 106.12 13.17-115.86108 CH 2 CHCH 2 170.83 12.62-117.12049 HCF ( 1 A') 32.44 9.97-138.30267 CH 2 CN 80.23 12.14-131.94867 CH 2 NC 79.89 12.51-131.91091 CHCO 48.39 11.70-151.77092 CH 2 CHO 110.37 11.76-153.02241 CH 3 CH 2 S 166.45 13.83-476.86312 HNO 37.30 9.93-130.37316 HO 2 ( 2 A" HOO) 37.97 9.97-150.79407 G2/97 cations CH 4 NH 3 92.60 12.11-39.99823 85.46 10.11-56.14074 OH 18.24 8.68-75.20208 OH 2 48.63 9.94-75.91586 FH 17.72 8.68-99.80005 SiH 4 78.23 11.76-291.06774 PH 13.40 8.68-341.08645 PH 2 PH 3 34.37 9.98-341.72911 62.17 10.35-342.36745 SH 14.41 8.68-397.94140 SH 2 ( 2 B 1 ) 36.12 9.98-398.59126 SH 2 ( 2 A 1 ) 34.12 10.05-398.50474 ClH 15.45 8.68-459.91043 C 2 H 2 C 2 H 4 68.45 9.71-76.82202 126.09 11.15-78.10994 CO 14.10 8.68-112.70217 N 2 ( 2 Σ) 12.79 8.68-108.86372 N 2 ( 2 Π) 11.63 8.68-108.82279 O 2 12.52 8.68-149.76399 S13

P 2 ( 2 Π) 4.02 9.01-681.47827 S 2 Cl 2 4.87 8.88-795.17918 4.11 9.00-919.08438 ClF 5.48 8.82-559.00587 CS 8.14 8.70-435.33395 BF 3 BCl 3 B 2 F 4 CO 2 CF 2 27.44 12.67-323.77052 18.87 14.58-1403.82082 47.99 19.92-448.55208 22.03 9.77-187.92172 22.60 10.31-237.11880 COS 22.74 10.48-510.60722 CS 2 CH 2 CH 3 C 2 H 5 15.14 10.92-833.23215 42.35 10.05-38.72239 81.16 9.98-39.43233 157.03 11.00-78.76626 C 3 H 4 (cyclopropene ) 131.80 13.36-116.12312 CH 2 =C=CH 2 135.45 12.97-116.15834 sec-c 3 H 7 227.55 15.38-118.06391 C 6 H 6 253.65 15.97-231.62524 C 6 H 5 CH 3 325.32 19.97-270.91466 CN 11.81 8.68-92.10519 CHO 42.90 9.03-113.45358 CH 2 OH 105.92 10.17-114.68765 CH 3 O 86.28 10.49-114.54994 CH 3 OH 122.13 11.58-115.22448 CH 3 F 86.80 10.48-139.17195 CH 2 S 60.84 10.41-436.65552 HSCH 2 90.46 10.56-437.30274 CH 3 SH 115.88 11.97-437.89193 CH 3 Cl 87.25 11.10-499.22101 C 2 H 5 OH 201.05 14.61-154.51884 CH 3 CHO 137.52 13.19-153.30818 CH 3 OF 103.75 13.13-214.26696 C 2 H 4 S (thiirane ) 139.22 11.90-475.94351 NCCN 39.48 12.69-184.96726 C 4 H 4 O (furan ) 179.52 12.69-229.45525 C 4 H 5 N (pyrrole ) 212.69 13.10-209.63566 C 6 H 5 OH 270.89 17.43-306.82532 C 6 H 5 NH 2 304.49 17.84-286.99566 B 2 H 4 100.44 11.98-51.59345 S14

NH 17.88 8.68-54.67659 NH 2 N 2 H 2 N 2 H 3 43.89 10.31-55.41868 68.38 10.24-110.19280 110.35 10.12-110.85512 HOF 35.51 9.97-174.95767 SiH 2 32.07 10.07-289.86352 SiH 3 60.75 10.35-290.52028 Si 2 H 2 38.42 11.09-578.97217 Si 2 H 4 85.32 14.73-580.20390 Si 2 H 5 103.43 16.38-580.82851 Si 2 H 6 127.66 19.08-581.40628 G2/97 anions CH 15.18 8.68-38.47539 CH 2 CH 3 39.90 9.95-39.12700 73.93 10.18-39.79617 NH 19.27 8.68-55.18277 NH 2 48.94 9.93-55.86008 OH 22.74 8.68-75.74901 SiH 10.49 8.68-289.61284 SiH 2 26.45 10.04-290.23666 SiH 3 48.49 10.33-290.86830 PH 13.67 8.68-341.49275 PH 2 35.61 9.98-342.13341 SH 15.30 8.68-398.40512 O 2 7.62 8.71-150.21824 NO 8.68 8.69-129.78504 CN 12.75 8.68-92.76464 PO 6.49 8.75-416.11401 S 2 Cl 2 3.68 9.09-795.58241 1.18 10.17-919.59332 CC (doublet) 9.63 8.69-75.94851 C 2 O (doublet CCO ) 24.44 9.94-151.18742 CF 2 ( 2 B 1 ) 12.49 10.97-237.54064 NCO (singlet) 28.51 9.45-167.97831 NO 2 (singlet ONO ) 21.11 10.18-204.99463 O 3 16.64 10.47-225.32874 OF (singlet) 5.21 8.84-174.83657 SO 2 15.94 10.74-548.14462 S 2 O 12.04 11.48-870.76398 C 2 H 38.40 9.47-76.62964 C 2 H 3 92.09 10.39-77.83596 S15

H 2 C=C=C 75.95 12.49-115.25817 H 2 C=C=CH 104.21 12.71-115.89601 CH 2 CHCH 2 163.43 13.98-117.13706 HCO 27.36 9.97-113.76059 HCF ( 2 A") 27.33 10.20-138.32011 CH 3 O 90.76 10.14-115.00571 CH 3 S 93.15 10.59-437.66037 CH 2 S 56.31 11.69-437.01491 CH 2 CN 78.67 12.27-132.00579 CH 2 NC 79.17 11.96-131.95423 CHCO 49.02 11.49-151.85725 CH 2 CHO 108.72 11.67-153.08924 CH 3 CO 105.03 12.98-153.04727 CH 3 CH 2 O 166.07 12.60-154.28537 CH 3 CH 2 S 166.71 13.26-476.93504 LiH 7.78 8.71-8.04522 HNO 33.55 9.98-130.38234 HO 2 ( 1 A' HOO ) 35.14 10.14-150.83206 protonated species NH 4 OH 3 C 2 H 3 SiH 5 PH 4 SH 3 ClH 2 H 3 G3/99' neutrals 128.27 9.98-56.85470 89.23 10.19-76.65527 90.98 11.09-77.49351 105.86 12.06-291.72606 91.66 10.39-343.03855 65.65 10.10-399.25446 39.33 9.97-460.60012 49.35 9.92-1.35021 C 4 H 6 (methyl allene) 216.95 15.74-155.79171 C 5 H 8 (isoprene) 294.12 17.78-195.08706 C 5 H 10 (cyclopentane) 361.50 14.12-196.33576 C 5 H 12 (n-pentane) 411.86 21.76-197.55099 C 5 H 12 (neopentane) 405.02 22.97-197.55817 C 6 H 8 (1,3-cyclohexadiene) 315.43 16.49-233.14953 C 6 H 8 (1,4-cyclohexadiene) 315.08 16.67-233.14892 C 6 H 12 (cyclohexane) 439.45 17.90-235.61648 C 6 H 14 (n-hexane) 487.75 24.76-236.82114 C 6 H 14 (3-methyl pentane) 484.37 25.18-236.82220 C 6 H 5 CH 3 (toluene) 330.26 18.90-271.24457 C 7 H 16 (n-heptane) 558.16 29.04-276.09128 C 8 H 8 (cyclooctatetraene) 342.58 20.24-309.22192 C 8 H 18 (n-octane) 633.98 31.99-315.36143 S16

C 10 H 8 (naphthalene) 381.07 20.86-385.42797 C 10 H 8 (azulene) 375.64 21.85-385.37074 CH 3 COOCH 3 (acetic acid methyl ester) 233.96 18.17-268.14649 (CH 3 ) 3 COH (t-butanol) 350.49 20.37-233.45538 C 6 H 5 NH 2 (aniline) 302.59 18.13-287.28224 C 6 H 5 OH (phenol) 270.79 17.31-307.14085 C 4 H 6 O (divinyl ether) 231.37 17.75-230.96161 C 4 H 8 O (tetrahydrofuran) 301.02 15.77-232.21904 C 5 H 8 O (cyclopentanone) 313.04 17.46-270.29485 C 6 H 4 O 2 (benzoquinone) 220.05 19.42-381.06308 C 4 H 4 N 2 (pyrimidine) 199.94 13.64-264.03476 C 2 H 6 O 2 S (dimethyl sulphone) 218.93 19.38-627.84324 C 6 H 5 Cl (chlorobenzene) 235.01 17.23-691.14294 N=C-CH 2 -CH 2 -C=N (butanedinitrile) 189.51 19.14-264.02367 C 4 H 4 N 2 (1,4-dipyridine) (pyrazine) 198.94 13.66-264.02780 CH 3 -C(=O)-CCH 169.12 17.46-229.73793 CH 3 -CH=CH-CHO (crotonaldehyde) 231.60 17.97-230.99735 CH 3 -C(=O)-O-C(=O)-CH 3 (acetic anhydride) 255.15 23.77-381.38455 C 4 H 6 S (2,5-dihydrothiophene) 231.25 15.48-553.60988 (CH 3 ) 2 CH-CN 265.77 18.17-211.15716 CH 3 -CO-CH 2 -CH 3 (methyl ethyl ketone) 291.34 19.42-232.23753 (CH 3 ) 2 CH-CHO 290.80 19.36-232.22813 C 4 H 8 O 2 (cyc-ch2-ch2-o-ch2-ch2-o (para)) (1,4-dioxane) 318.17 16.20-307.37503 C 4 H 8 S (tetrahydrothiophene) 293.53 16.32-554.84435 (CH 3 ) 3 C-Cl (t-butyl chloride) 317.79 19.48-617.46286 CH 3 -CH 2 -CH 2 -CH 2 -Cl (n-butyl chloride) 318.60 20.18-617.45220 C 4 H 8 NH (tetrahydropyrrole) 335.32 15.74-212.36098 CH 3 -CH 2 -CH(CH 3 )-NO 2 (2-nitrobutane) 348.64 24.39-362.62954 CH 3 -CH 2 -O-CH 2 -CH 3 (diethyl ether) 351.56 20.89-233.43332 CH 3 -CH(OCH 3 ) 2 (acetaldehyde dimethyl acetal) 366.09 23.19-308.59088 (CH 3 ) 3 C-SH (t-butanethiol) 338.23 21.37-556.05945 CH 3 -CH 2 -S-S-CH 2 -CH 3 (diethyl disulfide) 347.36 27.00-953.83239 (CH 3 ) 3 C-NH 2 (t-butylamine) 384.48 20.40-213.59279 Si(CH 3 ) 4 (tetramethylsilane) 377.41 27.97-448.61782 C 5 H 6 S cyc-ch=ch-s-c(ch 3 )=CH- (2-methyl thiophene) 243.66 17.88-591.68432 cyc-ch=ch-n(ch 3 )-CH=CH- (N-methyl pyrrole) 285.64 17.16-249.20335 C 5 H 10 O (tetrahydropyran) 378.40 17.06-271.49678 CH 3 -CH 2 -CO-CH 2 -CH 3 (diethyl ketone) 362.71 23.71-271.50788 C 5 H 10 O 2 CH 3 -C(=O)-O-CH(CH 3 ) 2 (Isopropyl acetate) 377.28 25.47-346.69640 C 5 H 10 S (tetrahydrothiopyran) 369.01 18.64-594.11818 cyc-c 5 H 10 NH (piperidine) 410.59 17.63-251.63931 S17

(CH 3 ) 3 C-O-CH 3 (t-butyl methyl ether) 423.82 23.74-272.70683 C 6 H 4 F 2 (1,3-difluorobenzene) 218.32 18.27-430.32187 C 6 H 4 F 2 (1,4-difluorobenzene) 217.41 18.37-430.32060 C 6 H 5 F (fluorobenzene) 238.56 16.26-331.14684 (CH 3 ) 2 CH-O-CH(CH 3 ) 2 (di-isopropyl ether) 495.48 27.73-311.98208 PF 5 43.63 16.98-840.04796 SF 6 55.45 13.56-996.42941 SCl 2 7.78 12.43-1317.29771 POCl 3 25.48 17.92-1795.53512 PCl 5 22.90 23.62-2639.86888 Cl 2 O 2 S 32.77 16.26-1467.63210 PCl 3 12.72 16.10-1720.32798 Cl 2 S 2 12.47 16.46-1715.08664 SiCl 2 7.23 12.60-1208.69265 CF 3 Cl 40.02 13.91-797.18433 C 2 F 6 78.13 20.24-674.83422 CF 3 32.39 11.51-337.33913 C 6 H 5 (phenyl radical) 225.37 14.27-231.27566 RR49 Me 76.81 10.50-39.79360 Et 153.13 12.91-79.06538 i-pr 226.35 16.50-118.33960 CH 2 =CH 2 131.44 10.53-78.49999 Me CH 2 CH 2 Et CH 2 CH 2 i-pr CH 2 CH 2 227.96 15.23-118.33501 301.63 18.56-157.60542 373.72 21.97-196.87841 S=CH 2 63.62 10.23-437.00115 Me SCH 2 Et SCH 2 i-pr SCH 2 158.51 15.96-476.84619 233.52 18.86-516.11777 304.51 22.79-555.39126 O=CH 2 69.43 10.02-114.40450 Me OCH 2 Et OCH 2 i-pr OCH 2 170.38 14.28-154.21753 243.77 17.35-193.49241 316.03 20.65-232.76822 CH 2 =CHMe 205.93 13.19-117.77387 Me CH 2 C HMe 300.40 19.53-157.60950 CH 2 =CMe 2 277.26 16.84-157.04941 Me CH 2 C Me 2 375.15 22.66-196.88532 S=CHMe 138.15 13.07-476.28007 Me SC HMe 233.10 19.61-516.11905 S=CMe 2 209.49 17.54-515.55832 Me SC Me 2 306.92 22.92-555.39317 S18

O=CHMe 143.46 12.73-153.68673 Me OC HMe 244.36 17.72-193.49436 O=CMe 2 215.50 16.81-192.96714 Me OC Me 2 316.69 21.00-232.76911 CH 2 =CHCN 131.64 13.52-170.64564 Me CH 2 C HCN 229.29 18.71-210.49420 CH 2 =CHF 114.10 11.34-177.67626 Me CH 2 C HF 212.42 16.54-217.51340 CH 2 =CHOMe 220.68 15.08-192.92691 Me CH 2 C HOMe 318.42 20.93-232.76420 CH 2 =CHNH 2 178.47 13.02-133.81229 Me CH 2 C HNH 2 277.67 17.89-173.65227 CH 2 =CHCHO 158.76 14.10-191.72156 Me CH 2 C HCHO 258.57 18.81-231.57046 CH 2 =CF 2 95.75 12.30-276.85728 Me CH 2 C F 2 196.61 17.40-316.70213 CH 4 115.64 10.03-40.47483 Me CH 2 CH 3 265.28 14.78-119.01080 Et CH 2 CH 3 338.65 18.19-158.28090 i-pr CH 2 CH 3 412.30 21.29-197.55301 Me SCH 3 194.06 15.80-477.50927 Et SCH 3 269.21 18.98-516.78000 i-pr SCH 3 340.98 22.57-556.05334 Me OCH 3 206.29 13.94-154.88422 Et OCH 3 280.16 16.98-194.15881 i-pr OCH 3 351.78 20.53-233.43289 Me CH 2 CH 2 CN 264.95 18.40-211.15589 Me CH 2 CH 2 F 248.69 16.11-218.18541 Me CH 2 CH 2 OMe 353.53 20.34-233.42867 Me CH 2 CH 2 NH 2 313.75 17.62-174.31225 Me CH 2 CH 2 CHO 290.98 19.17-232.22669 Me CH 2 CHF 2 231.76 17.07-317.37527 EtH 192.94 11.64-79.74094 t-bu 299.54 19.97-157.61556 t-buh 339.96 17.47-158.28363 F 3 C 32.39 11.51-337.33913 F 3 CH 66.65 11.59-338.02111 Cl 3 C 19.22 14.32-1417.30571 Cl 3 CH 52.31 14.26-1417.96634 MeO 2 CCH 2 198.55 17.57-267.47687 MeO 2 CCH 3 233.96 18.17-268.14649 NCC Me 2 227.31 19.73-210.50114 S19

NCCHMe 2 265.77 18.17-211.15716 PR8 Cyclobutene 223.31 12.76-155.79273 cis-1,3,5-hexatriene 308.26 20.16-233.12309 o-xylylene 341.49 20.64-309.24117 1,3-Pentadiene 294.12 18.31-195.08410 1,3-Cyclopentadiene 238.21 13.67-193.87611 1,5-Hexadiene 366.00 22.21-234.34632 1,3-Butadiene 220.78 14.81-155.81203 Ethylene 131.44 10.53-78.49999 1,3-Cyclohexadiene 315.43 16.49-233.14953 Benzocyclobutane 347.33 18.65-309.26105 Cyclohexene 377.36 17.27-234.38166 Norbornene 394.37 16.74-272.42344 PR8-1 TS 216.18 12.61-155.73922 PR8-2 TS 305.81 17.38-233.07516 PR8-3 TS 336.93 19.00-309.19784 PR8-4 TS 284.25 15.01-195.02176 PR8-5 TS 231.30 12.73-193.83112 PR8-6 TS 364.43 18.23-234.29204 PR8-7 TS 360.19 19.94-234.27754 PR8-8 TS 379.94 19.52-272.35021 Table S3. Deviations (kj mol 1 ) from Experimental and W1 Values. Property W4/08 AE Deviation B 2 H 6-3.82 BHF 2-2.02 BF 3-1.96 C 2 H 6-0.43 H 2 CN 0.50 NCCN -0.48 CH 2 NH 2-0.82 CH 3 NH -0.36 CH 3 NH 2-0.61 CF 2 0.92 N 2 H -0.25 N 2 H 2 0.14 N 2 H 4-1.16 FO 2-1.51 F 2 O 2-2.90 AlF 3 0.72 Si 2 H 6-1.85 P 4-4.02 S20

SO 2-0.89 SO 3-1.71 OCS 1.79 CS 2 2.65 S 2 O -1.22 S 3-0.99 S 4-2.34 BeCl 2-1.14 CCl 2 1.19 AlCl 3-0.58 ClCN 0.83 OClO -0.34 ClOO -4.65 Cl 2 O 0.01 H 2 1.52 OH 0.48 HF 0.53 H 2 O -0.29 CH 1.28 CH 2 0.32 CH 3 0.31 CH 4-0.13 C 2 H -1.08 C 2 H 2-0.54 NH 3-0.70 C 2 0.79 N 2 0.28 CO 1.37 CN -0.01 NO 0.95 O 2 0.83 OF 0.03 F 2-0.60 PH 3-1.73 HS -0.26 H 2 S -0.46 HCl -0.36 SO 0.93 ClO -1.35 ClF 0.27 P 2-0.07 S 2 0.35 Cl 2-0.44 Be 2 1.57 B 2-1.04 S21

BH 1.12 BH 3-1.68 BN (singlet) 1.96 BF 0.32 NH 0.95 NH 2 0.00 HCN -0.04 HOF -0.79 AlH 1.02 AlH 3 1.32 AlF 0.90 AlCl 0.54 SiH 0.76 SiH 4-0.38 SiO 0.29 SiF 0.93 CS 2.52 BN (triplet) -0.31 CF 1.28 BeF 2-1.21 CH 2 C 0.34 CH 2 CH 0.72 C 2 H 4 0.23 CH 2 NH 0.18 HCO 1.08 H 2 CO 0.79 CO 2 0.52 HNO 0.72 NO 2 0.95 N 2 O 0.23 O 3-1.67 HO 2 0.11 H 2 O 2-0.96 F 2 O -0.77 HOCl -0.46 S 2 H -0.86 DBH24 ΔH DBH24-1 fwd -0.12 DBH24-2 fwd 0.80 DBH24-3 fwd -0.08 DBH24-4 fwd 0.61 DBH24-5 fwd 0.78 DBH24-6 fwd 1.38 DBH24-7 fwd -0.05 DBH24-8 fwd -0.22 DBH24-9 fwd -1.08 DBH24-10 fwd 1.48 S22

DBH24-11 fwd 0.22 DBH24-12 fwd -0.05 DBH24-1 rev 0.23 DBH24-2 rev 0.80 DBH24-3 rev -1.23 DBH24-4 rev 0.61 DBH24-5 rev 0.12 DBH24-6 rev 1.44 DBH24-7 rev -0.27 DBH24-8 rev -0.69 DBH24-9 rev -0.76 DBH24-10 rev 1.23 DBH24-11 rev 1.09 DBH24-12 rev 1.74 HB16 HB ClHNH 3-1.24 COHF 0.18 FHNH 3-0.53 H 2 OH 2 O -0.21 HClHCl -0.19 HFH 2 O -0.21 HFHF -0.25 HFHCN -0.08 NH 3 NH 3-0.20 NH 3 H 2 O -0.24 OCHF -0.11 H 3 OH 2 O -0.96 NH 4 H 2 O -0.27 HCCH 2 O -0.86 CNH 2 O -0.50 OHH 2 O -0.79 WI9/04 BE HeNe -0.23 HeAr -0.27 NeNe -0.40 NeAr -0.42 CH 4 Ne -0.33 C 6 H 6 Ne -0.55 CH 4 CH 4-0.48 C 2 H 2 C 2 H 2 0.11 C 2 H 4 C 2 H 4-0.07 G2/97' ΔH f LiH -0.22 BeH -1.10 CH 2 ( 1 A 1 ) -1.08 SiH 2 ( 1 A 1 ) -2.85 S23

SiH 2 ( 3 B 1 ) -1.55 SiH 3-1.50 PH 2-0.45 Li 2 1.86 LiF -0.54 H 3 COH -0.04 Na 2 0.71 Si 2-1.08 NaCl 0.53 CH 3 Cl -0.03 H 3 CSH -0.24 BCl 3 1.37 CF 4-0.27 CCl 4-0.36 COF 2 3.95 SiF 4-1.28 SiCl 4-0.24 ClNO 0.71 NF 3-0.58 PF 3-0.43 ClF 3-0.18 C 2 F 4-3.02 C 2 Cl 4-3.32 CF 3 CN -0.34 CH 3 CCH (propyne) 0.40 CH 2 =C=CH 2 (allene) -0.77 C 3 H 4 (cyclopropene) 1.51 CH 3 CH=CH 2 (propylene) -0.13 C 3 H 6 (cyclopropane) 0.44 C 3 H 8 (propane) -0.24 CH 2 CHCHCH 2 (butadiene) -0.17 C 4 H 6 (2-butyne) 0.95 C 4 H 6 (methylene cyclopropane) -1.90 C 4 H 6 (bicyclobutane) 1.79 C 4 H 6 (cyclobutene) 1.20 C 4 H 8 (cyclobutane) -0.55 C 4 H 8 (isobutene) -0.38 C 4 H 10 (trans butane) -0.02 C 4 H 10 (isobutane) 0.08 C 5 H 8 (spiropentane) 0.04 C 6 H 6 (benzene) -0.30 CH 2 F 2-0.42 CHF 3-0.10 S24

CH 2 Cl 2 0.31 CHCl 3 0.35 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) -0.85 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) -0.07 C 2 H 4 O (oxirane) -0.22 CH 3 CHO (acetaldehyde) -0.09 HCOCOH (glyoxal) -0.80 CH 3 CH 2 OH (ethanol) 0.27 CH 3 OCH 3 (dimethylether) -0.18 C 2 H 4 S (thiirane) -1.63 (CH 3 ) 2 SO (dimethyl sulfoxide) 0.03 C 2 H 5 SH (ethanethiol) -0.16 CH 3 SCH 3 (dimethyl sulfide) -0.90 CH 2 =CHF (vinyl fluoride) -0.87 C 2 H 5 Cl (ethyl chloride) 0.24 CH 2 =CHCl (vinyl chloride) -3.97 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) -0.19 (CH 3 ) 2 CHOH (isopropanol) 0.24 C 2 H 5 OCH 3 (methyl ethyl ether) -0.44 (CH 3 ) 3 N (trimethylamine) -0.27 C 4 H 4 O (furan) 0.44 C 4 H 4 S (thiophene) -2.04 C 4 H 5 N (pyrrole) 0.24 C 5 H 5 N (pyridine) -0.59 C 2 H 3 ( 2 A') -1.50 CH 3 CO ( 2 A') -0.58 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

CH 3 S ( 2 A') 0.01 C 2 H 5 ( 2 A') 0.04 (CH 3 ) 2 CH ( 2 A') -0.32 (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 -1.72 C -1.77 N -1.23 O -0.38 F 0.04 Ne 0.56 Na 0.00 Mg -0.24 Al 0.04 Si -1.14 P -1.67 S -2.82 Cl -1.96 Ar -1.25 CH 4 2.54 NH 3-0.01 OH -1.03 OH 2-0.64 FH 0.20 SiH 4 0.74 PH -0.62 PH 2-1.22 PH 3-0.67 SH -1.36 SH 2 ( 2 B 1 ) -1.35 SH 2 ( 2 A 1 ) -0.81 ClH -0.84 C 2 H 2 0.29 C 2 H 4 1.19 CO 0.64 N 2 ( 2 Σ) -0.81 N 2 ( 2 Π) -1.23 O 2-0.57 P 2 ( 2 Π) -0.49 S 2 0.24 Cl 2-0.63 ClF -0.74 S26

CS 1.60 BF 3 2.35 BCl 3-2.03 B 2 F 4-8.76 CO 2-0.89 CF 2-0.16 COS -0.52 CS 2 0.32 CH 2-0.24 CH 3 0.76 C 2 H 5 1.46 cyclopropene -0.08 CH 2 =C=CH 2 1.48 sec-c 3 H 7 3.33 C 6 H 6 2.12 C 6 H 5 CH 3 2.27 CN -0.95 CHO 0.85 CH 2 OH 0.04 CH 3 O -0.14 CH 3 OH 0.96 CH 3 F 2.87 CH 2 S 0.01 HSCH 2-0.96 CH 3 SH 0.07 CH 3 Cl 1.03 C 2 H 5 OH -1.64 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 2 2.26 B 2 H 4-4.02 NH -0.78 NH 2 0.50 N 2 H 2 0.65 N 2 H 3 0.14 HOF -0.99 SiH 2 0.50 SiH 3 0.57 Si 2 H 2-1.29 S27

Si 2 H 4 1.18 Si 2 H 5 1.45 Si 2 H 6-2.64 G2/97 EA Li 2.97 B -3.71 C -3.53 O -0.61 F 2.22 Na 1.95 Al -1.80 Si -2.40 P -2.81 S -1.17 Cl -0.27 CH -2.48 CH 2 0.00 CH 3 0.46 NH -1.77 NH 2 0.62 OH 0.94 SiH -2.14 SiH 2-1.93 SiH 3 0.64 PH -2.30 PH 2-1.11 SH -1.42 O 2-1.70 NO -0.67 CN 1.52 PO -0.61 S 2-1.12 Cl 2 0.39 CC -1.96 CCO 0.22 CF 2 ( 2 B 1 ) -0.20 NCO -0.08 ONO 0.18 O 3 1.31 OF -0.66 SO 2 1.15 S 2 O 1.72 C 2 H 2.21 C 2 H 3 1.14 H 2 C=C=C 1.64 H 2 C=C=CH 1.78 S28

CH 2 CHCH 2 1.27 HCO 0.59 HCF ( 2 A") -0.34 CH 3 O 1.52 CH 3 S 1.03 CH 2 S -0.34 CH 2 CN 0.61 CH 2 NC 2.96 CHCO -0.18 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 -1.13 HOO ( 1 A') -0.35 G2/97 PA NH3 0.54 OH 2-1.20 C 2 H 2 0.50 SiH 4-1.91 PH 3 0.04 SH 2 0.21 ClH 0.30 H 2-0.63 G3/99' ΔH f methyl allene -0.37 isoprene -0.06 cyclopentane -0.36 n-pentane -0.48 neo pentane -1.26 1,3-cyclohexadiene -0.08 1,4-cyclohexadiene 0.61 cyclohexane 0.21 n-hexane -0.35 3-methyl pentane -0.53 toluene -0.53 n-heptane -1.09 cyclooctatetraene 0.00 n-octane -0.83 naphthalene -1.68 azulene 0.00 acetic acid methyl ester 0.94 t-butanol 0.03 aniline 0.21 phenol 0.98 S29

divinyl ether 0.88 tetrahydrofuran 0.51 cyclopentanone -0.15 benzoquinone 2.15 pyrimidine -2.11 dimethyl sulphone 0.38 chlorobenzene -0.94 butanedinitrile 0.37 1,4-dipyridine pyrazine 1.97 CH 3 -C(=O)-CCH 3.21 crotonaldehyde -0.65 acetic anhydride -0.03 2,5-dihydrothiophene -1.42 (CH 3 ) 2 CH-CN 1.70 methyl ethyl ketone 0.50 (CH 3 ) 2 CH-CHO 0.78 1,4-dioxane 0.18 tetrahydrothiophene -0.32 t-butyl chloride -0.40 n-butyl chloride 0.05 tetrahydropyrrole 0.45 2-nitrobutane -0.75 diethyl ether -0.19 acetaldehyde dimethyl acetal -0.30 t-butanethiol -1.14 diethyl disulfide 0.00 t-butylamine 0.16 tetramethylsilane 3.63 2-methyl thiophene -2.05 N-methyl pyrrole -0.12 tetrahydropyran 0.37 diethyl ketone -0.51 isopropyl acetate 0.47 tetrahydrothiopyran -0.57 piperidine 0.66 t-butyl methyl ether -0.40 1,3-difluorobenzene 0.82 1,4-difluorobenzene 0.83 fluorobenzene 0.45 di-isopropyl ether -0.55 PF 5-0.23 SF 6-2.31 SCl 2 0.55 POCl 3 1.90 PCl 5-1.52 Cl 2 O 2 S 1.99 PCl 3 1.71 Cl 2 S 2-1.66 S30

SiCl 2-0.80 CF 3 Cl -0.11 C 2 F 6 0.30 CF 3-1.53 phenyl radical 0.31 RR49 ΔH r ADD1 0.89 ADD2 0.24 ADD3-0.19 ADD4 1.65 ADD5 1.40 ADD6 1.11 ADD7 0.74 ADD8 0.47 ADD9 0.27 ADD10 0.17 ADD11 0.00 ADD12 1.55 ADD13 1.72 ADD14 0.40 ADD15-0.57 ADD16-0.07 ADD17-0.10 ADD18-0.12 ADD19 0.10 ADD20-0.21 ADD21-0.43 ABS1-0.34 ABS2-0.24 ABS3 0.45 ABS4 0.09 ABS5 0.20 ABS6 0.11 ABS7 0.18 ABS8 0.39 ABS9 0.70 ABS10-0.06 ABS11 0.40 ABS12 0.05 ABS13-0.47 ABS14 0.22 ABS15 0.62 ABS16 0.52 ABS17 0.37 ABS18 0.41 ABS19 0.20 ABS20 0.72 ABS21 0.83 ABS22-0.05 S31

ABS23-0.06 ABS24 0.59 ABS25 0.85 ABS26 0.52 ABS27 0.69 ABS28 0.89 PR8 ΔH PR8-1 -1.76 PR8-2 -0.85 PR8-3 -1.11 PR8-4 -0.44 PR8-5 0.05 PR8-6 -1.58 PR8-7 -0.51 PR8-8 -2.02 S32