TAE0 used for evaluating CCSD(T) composite Please note methods (a) cyclobutene 947.166 (b) t-butadiene 959.699 (b) cyclobutane 1080.856 (b) n-pentane 1496.829 (b) benzene 1305.434 (b) acetic 764.355 hclo4 313.861 (b) c2f6 769.966 (b) c2cl6 543.450 (b) n2o4 455.568 (b) cloocl 142.498 (b) clo3 159.898 (b) hoclo 192.058 (b) pf5 546.928 (b) (c) sf6 466.282 (b) oxadiazole 676.856 (b) dioxetan2one 723.294 (b) dioxetane 709.452 (b) dithiotane 646.567 (b) borole 1009.291 (b) c2cl4 457.586 (b) c2f4 573.984 (b) cis-c2f2cl2 513.940 (b) trans-c2f2cl2 514.302 (b) cyclopentadiene 1123.695 (b) formic-anhydride 729.046 (b) furan 950.569 (b) oxetane 893.178 (b) pyrrole 1020.691 (b) silole 1048.227 (b) thiophene 921.976 (b) beta-lactim 942.762 (b) clf5 174.846 (b) clf3 121.922 (b) pf3 358.178 (b) hoclo2 257.247 (b) h2no 258.268 (b) nh2oh 334.135 (b) cyclopropane 802.913 (b) cyclopropene 646.639 (b) ch3ph2 504.810 (b) nh2f 238.774 (b) cclh3 371.306 (b) clno 186.787 (b) tetrahedrane 755.795 (b) n-butane 1220.023 (b) c2cl2 341.197 (b) c2clh3 516.461 (b) c2clh5 650.112 (b) c2clh 365.341 (b) ccl2h2 351.127 (b) ccl2o 338.050 (b) ccl3h 329.795 (b) ccl4 305.340 (b) cf2cl2 380.820 (b) fno 210.159 (b) ch2clf 381.724 (b) chf3 441.984 (b) clcof 373.709 (b) formamide 539.298 (b) cyclobutadiene 782.290 (b) allyl 725.171 (b) cyclopropyl 695.541 (b) h2ccn 492.784 (b) oxirene 437.280 oxirane 615.020 dioxirane 388.920 ketene 513.100 acetaldehyde 642.580 formic 479.800 methanol 480.940 ethanol 760.680 glyoxal 610.970 t-hcoh 305.270 c-hcoh 300.860 hcnh 319.890 hocn 395.980 honc 336.830 hnco 420.730 hcno 352.230 c-n2h2 273.690 hnnn 318.060 hnc 288.270 t-hono 299.740 c-hono 299.310 nh2cl 230.540 t-hooo 220.740 (b) c-hooo 221.150 ch3f 397.680 ch2f2 416.000 cf4 465.500 sih3f 363.690 sif4 565.920 c2h3f 545.630 c2h5f 678.230 fccf 376.200 hccf 385.080 hcof 389.550 f2co 410.040 ch2-sing 170.870 propane 943.000 propene 811.560 propyne 670.470 allene 669.400 b2h6 567.530 bhf2 398.730 bf3 461.320 c2h6 666.280 h2cn 327.950 nccn 491.500 ch2nh2 451.020 ch3nh 444.220 ch3nh2 542.220 cf2 253.260 n2h 216.450 t-n2h2 278.680 n2h4 404.760 fo2 130.150 foof 146.000 alf3 423.480 si2h6 503.090 p4 285.960 so2 254.420 so3 336.120 ocs 328.650 cs2 274.670 s2o 203.580 s3 163.970 s4-c2v 228.150 ccl2 172.710 alcl3 305.600 clcn 278.790 oclo 122.320 cloo 121.880 cl2o 96.940 bn3pi 103.550 cf 130.350 ch2c 345.100 ch2ch 423.060 c2h4 532.110 ch2nh 414.410 hco 270.660 h2co 357.510 co2 381.940 hno 196.780 no2 221.610 n2o 263.430 o3 142.330 hoo 165.970 hooh 252.080 f2o 89.420 hocl 156.730 ssh 157.680 b2 65.850 bh 81.490 bh3 264.810 bn 102.620 bf 179.950 nh 78.340 nh2 170.580 hcn 303.210 hof 149.320 alh 70.840 alh3 200.910 alf 161.760 alcl 120.630 sih 70.650 sih4 304.160 sio 190.370 sif 140.620 cs 169.590 h2 103.280 oh 101.760 hf 135.270 h2o 219.320 ch 79.990 ch2-trip 179.860 ch3 289.080 ch4 392.460 cch 257.040 c2h2 388.700 nh3 276.530 c2 144.070 n2 225.000 co 256.150 cn 178.180 no 149.800 o2 117.960 of 51.170 f2 36.950 ph3 227.360 hs 83.680 h2s 173.580 hcl 102.200 so 123.700 clo 63.370 clf 60.280 p2 116.220 s2 101.770 cl2 57.070 (a) ZPVE-inclusive, all-electron, relativistic, DBOC-inclusive FCI/CBS total atomization energies at 0 K (TAE0) for comparison with experiment. (b) Note that the ZPVE values used for converting the W4 TAEe to TAE0 values are obtained by scaling harmonic DSD-PBEP86-D3BJ/aug’-cc-pV(Q+d)Z frequencies rather than from high-level ab initio anharmonic force field calculations as prescribed in the W4 protocol. These values should be treated with some caution. (c) In the accepted version of the manuscript this value was 545.734 kcal/mol due to an error in the scalar relativistic component. The incorrect scalar relativistic value was calculated at the CCSD(T)/AVTZ-DK level of theory. Using the correct CCSD(T)/AVQZ-DK scalar relativistic value results in a TAEe value of 546.928 kcal/mol.