Methylene-Neon size-extensivity calculation The UHF based calculations performed using the TZ2P basis set for CH2 and the cc-pVTZ basis set for Neon Methylene-neon geometry: Z-matrix input: C H 1 rCH H 1 rCH 2 HCH Ne 1 rINF 2 bisect 3 dih rCH = 1.0775 HCH = 133.29 rINF =100.00 bisect = 66.645 dih = 0.000 Nuclear Repulsion Energy = 6.5846523571 hartrees SF calculation using high-spin triplet reference EHF = -167.469817210 EMP2 = -167.870015899 Correlation Energy = -0.421915723 CCSD Total Energy = -167.891732933 EE calculation using singlet (closed-shell) reference EHF = -167.406743221 EMP2 = -167.824878993 Correlation Energy = -0.446045007 CCSD Total Energy = -167.852788228 --------------------------- Methylene (size-extensivity) calculations Equilibrium geometry used: (FCI/TZ2P) C H 1 rCH H 1 rCH 2 HCH rCH = 1.0775 HCH = 133.29 Nuclear Repulsion Energy = 6.1608618178 hartrees SF calculation using high-spin triplet reference EHF = -38.937955569 EMP2 = -39.060862657 Correlation Energy = -0.142963229 CCSD Total Energy = -39.080918798 EE calculation using singlet (closed-shell) reference EHF = -38.874881580 EMP2 = -39.015725751 Correlation Energy = -0.167092513 CCSD Total Energy = -39.041974093 --------------------------- --------------------------- Methylene: Adiabatic excitation energies FCI/TZ2P optimized geometries used. The TZ2P basis set and high-spin UHF reference used for the single point calculations ---------------------- The geometry for triplet (reference) state: 3B1 is same as in the size-extensivity calculation ------- a 1A1 state geometry: C H 1 rCH H 1 rCH 2 HCH rCH = 1.1089 HCH = 101.89 Nuclear Repulsion Energy = 6.0337753316 hartrees EHF = -38.919791792 EMP2 = -39.043043599 Correlation Energy = -0.143390973 CCSD Total Energy = -39.063182765 ------- b 1B1 state geometry: C H 1 rCH H 1 rCH 2 HCH rCH = 1.0748 HCH = 141.56 Nuclear Repulsion Energy = 6.1688997427 hartrees EHF = -38.936751546 EMP2 = -39.059890913 Correlation Energy = -0.143347464 CCSD Total Energy = -39.080099010 ------- c 1A1 state geometry: C H 1 rCH H 1 rCH 2 HCH rCH = 1.0678 HCH = 170.08 Nuclear Repulsion Energy = 6.1956449370 hartrees EHF = -38.927357576 EMP2 = -39.051124228 Correlation Energy = -0.144656239 CCSD Total Energy = -39.072013815 --------------------------- --------------------------- Nitrenium: The CISD/TZ2P(f,d) optimized geometries used The TZ2Pf basis set and high-spin UHF reference used for the single point calculations ------- 3B1 (reference) state geometry: N H 1 rNH H 1 rNH 2 HNH rNH = 1.0295 HNH = 150.88 Nuclear Repulsion Energy = 7.4617278181 hartrees EHF = -55.236748697 EMP2 = -55.383288172 Correlation Energy = -0.166553276 CCSD Total Energy = -55.403301973 ------- a 1A1 state geometry: N H 1 rNH H 1 rNH 2 HNH rNH = 1.0459 HNH = 107.96 Nuclear Repulsion Energy = 7.3961310239 hartrees EHF = -55.211387188 EMP2 = -55.359560032 Correlation Energy = -0.167768985 CCSD Total Energy = -55.379156174 ------- b 1B1 state geometry: N H 1 rNH H 1 rNH 2 HNH rNH = 1.0293 HNH = 161.47 Nuclear Repulsion Energy = 7.4580461860 hartrees EHF = -55.236144178 EMP2 = -55.382667311 Correlation Energy = -0.166772828 CCSD Total Energy = -55.402917006 ------- c 1A1 state geometry: N H 1 rNH H 1 rNH 2 HNH rNH = 1.0315 HNH = 180.00 Nuclear Repulsion Energy = 7.4387489642 hartrees EHF = -55.235010510 EMP2 = -55.381564553 Correlation Energy = -0.167042120 CCSD Total Energy = -55.402052630 --------------------------- --------------------------- Cyclobutadiene: CCSD(T)/cc-pVTZ optimized Singlet (X^1A_g) geometry; point group: D2h Z matrix input: C C 1 ccs C 2 ccd 1 ccc C 3 ccs 2 ccc 1 dihh H 1 hc 2 hccs 3 dihc H 2 hc 3 hccd 4 dihc H 3 hc 4 hccs 1 dihc H 4 hc 1 hccd 2 dihc ccs 1.566000 ccd 1.343000 hc 1.074000 ccc 90.000 hccs 134.910 hccd 135.090 dihh 0.000 dihc 180.000 Nuclear Repulsion Energy = 98.8821560064 hartrees Single point calculation using cc-pVTZ basis set: 1. High spin ROHF reference (SF calculation) EHF = -153.658702689 EMP2 = -154.344410890 Correlation Energy = -0.705879311 CCSD Total Energy = -154.364582000 2. RHF reference (EE calculation) EHF = -153.695315728 EMP2 = -154.388889871 Correlation Energy = -0.721608906 CCSD Total Energy = -154.416924635 --------------------------- Cyclobutadiene: CCSD(T)/cc-pVTZ optimized Triplet (^3A_2g) geometry; point group: D4h Z matrix input: C C 1 cc C 2 cc 1 ccc C 3 cc 2 ccc 1 dihc H 1 hc 2 hcc 3 dihh H 2 hc 3 hcc 4 dihh H 3 hc 4 hcc 1 dihh H 4 hc 1 hcc 2 dihh cc 1.439000 ccc 90.000 ccc 90.000 dihc 0.000 hc 1.073000 hcc 135.000 dihh 180.000 Nuclear Repulsion Energy = 99.4931915115 hartrees Single point calculation using the cc-pVTZ basis set: High spin ROHF reference EHF = -153.697275181 EMP2 = -154.378239017 Correlation Energy = -0.702582178 CCSD Total Energy = -154.399857359 --------------------------- --------------------------- Benzynes: All geometries optimized at the SF-TDDFT/6-31G* level using 50/50 functional --------------------------- ortho-benzyne; SF calculation, singlet geometry Cartesian coordinates: H 2.518466 .000000 -.131102 C 1.443350 .000000 -.129071 C .698800 .000000 1.050271 H 1.218994 .000000 1.994214 C -.698800 .000000 1.050271 H -1.218994 .000000 1.994214 C -1.443350 .000000 -.129071 H -2.518466 .000000 -.131102 C -.620604 .000000 -1.229469 C .620604 .000000 -1.229469 Nuclear Repulsion Energy = 189.1020524482 hartrees Single point calculation using the cc-pVTZ basis, ROHF reference 6 core and 5 virtuals frozen EHF = -229.435002175 EMP2 = -230.305244473 Correlation Energy = -0.900732418 CCSD Total Energy = -230.335734593 --------------------------- ortho-benzyne; SF calculation at triplet geometry Cartesian coordinates: H 2.476058 .000000 -.120773 C 1.397826 .000000 -.115266 C .690428 .000000 1.085671 H 1.229929 .000000 2.017939 C -.690428 .000000 1.085671 H -1.229929 .000000 2.017939 C -1.397826 .000000 -.115266 H -2.476058 .000000 -.120773 C -.692326 .000000 -1.284303 C .692326 .000000 -1.284303 Nuclear Repulsion Energy = 186.7796773895 hartrees Single point calculation using the cc-pVTZ basis, ROHF reference 6 core and 5 virtuals frozen EHF = -229.464419607 EMP2 = -230.335995778 Correlation Energy = -0.902451276 CCSD Total Energy = -230.366870882 --------------------------- --------------------------- meta-benzyne singlet geometry Cartesian coordinates: H -2.14490 .000000 -1.09181 C -1.16532 .000000 -.64614 C .00000 .000000 -1.40225 H .00000 .000000 -2.48201 C 1.16532 .000000 -.64614 H 2.14490 .000000 -1.09181 C 1.00834 .000000 .70681 C -.00000 .000000 1.60963 H .00000 .000000 2.68230 C -1.00834 .000000 .70681 Nuclear Repulsion Energy = 188.8101975912 hartrees Single point calculation using the cc-pVTZ basis, ROHF reference 6 core and 5 virtuals frozen EHF = -229.430389476 EMP2 = -230.308022286 Correlation Energy = -0.907594672 CCSD Total Energy = -230.337984148 --------------------------- meta-benzyne triplet geometry Cartesian coordinates: H -2.14689 .000000 1.16892 C -1.21423 .000000 .63214 C .00000 .000000 1.31213 H .00000 .000000 2.39042 C 1.21423 .000000 .63214 H 2.14689 .000000 1.16892 C 1.15425 .000000 -.73302 C .00000 .000000 -1.47122 H .00000 .000000 -2.54931 C -1.15425 .000000 -.73302 Nuclear Repulsion Energy = 187.2036581675 hartrees Single point calculation using the cc-pVTZ basis, ROHF reference 6 core and 5 virtuals frozen EHF = -229.468482368 EMP2 = -230.341646471 Correlation Energy = -0.904396023 CCSD Total Energy = -230.372878391 --------------------------- --------------------------- para-benzyne, singlet geometry Cartesian coordinates: H 2.145810 -1.225292 .000000 C 1.201382 -.709285 .000000 C 1.201382 .709285 .000000 H 2.145810 1.225292 .000000 C .000000 1.335664 .000000 C -1.201382 .709285 .000000 H -2.145810 1.225291 .000000 C -1.201382 -.709285 .000000 H -2.145810 -1.225291 .000000 C .000000 -1.335664 .000000 Nuclear Repulsion Energy = 187.2138176166 hartrees Single point calculation using the cc-pVTZ basis, ROHF reference 6 core and 5 virtuals frozen EHF = -229.323462213 EMP2 = -230.271497449 Correlation Energy = -0.944194859 CCSD Total Energy = -230.267657072 --------------------------- para-benzyne, triplet geometry Cartesian coordinates: H 2.144994 -1.255165 .000000 C 1.222802 -.697850 .000000 C 1.222802 .697850 .000000 H 2.144994 1.255165 .000000 C .000000 1.308815 .000000 C -1.222802 .697850 .000000 H -2.144994 1.255165 .000000 C -1.222802 -.697850 .000000 H -2.144994 -1.255165 .000000 C .000000 -1.308815 .000000 Nuclear Repulsion Energy = 187.1095116544 hartrees Single point calculation using the cc-pVTZ basis, ROHF reference 6 core and 5 virtuals frozen EHF = -229.325640757 EMP2 = -230.272834548 Correlation Energy = -0.943582987 CCSD Total Energy = -230.269223744 --------------------------- --------------------------- 1,2,3 tri-dehydro benzene geometries optimised at the B3LYP/cc-pVTZ level --------------------------- 123 tdb a1 state geometry Cartesian coordinates: C 0.000000 0.000000 -1.793841 C -0.849111 0.000000 -0.745315 C -1.176517 0.000000 0.593267 C 0.000000 0.000000 1.370669 C 0.849111 0.000000 -0.745315 C 1.176517 0.000000 0.593267 H 0.000000 0.000000 2.458558 H 2.186826 0.000000 0.980780 H -2.186826 0.000000 0.980780 Nuclear Repulsion Energy = 181.0693398559 hartrees Calculation using 6-31g*; ROHF reference EHF = -228.533195959 EMP2 = -229.257492549 Correlation Energy = -0.764758228 CCSD Total Energy = -229.297954187 Calculation using cc-pVTZ; ROHF reference EHF = -228.607890941 EMP2 = -229.554938572 Correlation Energy = -0.977392638 CCSD Total Energy = -229.585283578 --------------------------- 123 tdb b1 state geometry Cartesian coordinates: C 0.00000000 0.00000000 -1.38834577 C -1.17584707 0.00000000 -0.85624325 C -1.23856822 0.00000000 0.53917710 C 0.00000000 0.00000000 1.21273174 C 1.17584707 0.00000000 -0.85624325 C 1.23856821 0.00000000 0.53917710 H 0.00000000 0.00000000 2.29726826 H 2.16873946 0.00000000 1.09331604 H -2.16873946 0.00000000 1.09331604 Nuclear Repulsion Energy = 179.5144623175 hartrees Calculation using 6-31g*; ROHF reference EHF = -228.699091358 EMP2 = -229.400285213 Correlation Energy = -0.744456671 CCSD Total Energy = -229.443548029 Calculation using cc-pVTZ; ROHF reference EHF = -228.771218840 EMP2 = -229.692524827 Correlation Energy = -0.956465975 CCSD Total Energy = -229.727684814 --------------------------- --------------------------- Ethane (C-C bond breaking) --------------------------- The methyl groups were frozen at the planar staggered configuration and the C-C bond distance was varied from 1.05836 angstroms to 5.29180 High-spin triplet UHF reference was employed during the calculations and aug-cc-pVTZ basis was used. The geometry for the first point is as follows: C C 1 CCX H 1 CH 2 A90 H 1 CH 2 A90 3 A120 H 1 CH 2 A90 4 A120 H 2 CH 1 A90 3 D180 H 2 CH 1 A90 6 A120 H 2 CH 1 A90 7 A120 CH=1.084819 A90=90. A120=120. CCX=1.05836 (varied for other points) D180=180. $end The Nuclear repulsion energies and EHF and ECCSD for a few points is as follows as follows CCX Nuc.Rep.Energy EHF ECCSD 1.05836 52.5729405146 -78.417026801 -78.826832539 1.69338 42.1290049798 -78.935149354 -79.324076976 2.32839 36.5836838084 -79.108242600 -79.478051690 3.17508 32.2874705744 -79.149691223 -79.513147086 5.29180 27.2426484019 -79.155290323 -79.516941077