Manuscript No ... The Fragementation of Benzyl- and Alkoxychlorocarbenes in Hydrocarbon Solvents and in Argon Matrices. Reassessment of the Mechanism(s) of ROCCl Fragmentations by Robert A. Moss, Yan Ma, Fengmei Zheng, and Ronald Sauers Departement of Chemistry and Chemical Biology Rutgers, The State University of New Jersey, New Brunswick, NJ 08903 Thomas Bally* and Alexander Maltsev Department of Chemistry, University of Fribourg, Perolles, CH-1700 Fribourg, Switzerland and John P. Toscano and Brett M. Showalter Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218 SUPPORTING INFORMATION ********************* Energies and geometries of all stationary points located and characterized in the course of the above study Note: All structures are optimized in vacuum, with energies in hartree, unless otherwise noted. If no "low frequencies" are given, the stationary points are potential energy minima. ******************************************** * * * Calculations on CH3-O-C-Cl * * * ******************************************** trans-CH3OCCl Symmetry: CS Method: B3LYP Basis set: 6-31G* State 1-A'/E(B3LYP)=-613.3456837 CCSD(T)/cc-pVDZ=-612.4073651 (single point) CCSD(T)/cc-pVTZ=-612.639923 (single point) CHelpG charges: 6 -2.239919 0.052748 0.000000 * 0.356262 1 -2.689804 -0.378635 0.895791 * -0.014521 1 -2.689804 -0.378635 -0.895791 * -0.014521 1 -2.316502 1.141392 0.000000 * -0.038096 8 -0.839649 -0.334824 0.000000 * -0.032349 6 0.000000 0.652705 0.000000 * -0.169633 17 1.638401 -0.114015 0.000000 * -0.087143 Zero-point correction= 0.046663 Thermal correction to Energy= 0.051620 Thermal correction to Enthalpy= 0.052565 Thermal correction to Gibbs Free Energy= 0.018822 ---------------------------------------------------- trans-CH3OCCl Symmetry: CS Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM,MeCN)=-613.351974 CHelpG charges: 1 -2.680462 -.467092 .897656 * -0.116537 6 -2.263876 -.012117 .000003 * 0.746090 8 -.833896 -.336926 -.000004 * -0.107818 6 -.033457 .662264 -.000003 * -0.133492 17 1.659136 -.078922 .000001 * -0.150569 1 -2.680469 -.467086 -.897649 * -0.116538 1 -2.389216 1.070376 .000007 * -0.121137 Zero-point correction= 0.046407 Thermal correction to Energy= 0.051479 Thermal correction to Enthalpy= 0.052423 Thermal correction to Gibbs Free Energy= 0.018423 ---------------------------------------------------- trans-CH3OCCl Symmetry: CS Method: MP2 Basis set: 6-31G* State 1-A'/E(MP2)=-612.285429 CCSD(T)/cc-pVDZ=-612.4071946 (single point) 6 -2.225469 0.012351 0.000000 1 -2.668054 -0.421185 0.895503 1 -2.668054 -0.421185 -0.895503 1 -2.297859 1.098964 0.000000 8 -0.820066 -0.374093 0.000000 6 0.000000 0.637544 0.000000 17 1.620430 -0.068425 0.000000 Zero-point correction= 0.047831 Thermal correction to Energy= 0.052702 Thermal correction to Enthalpy= 0.053646 Thermal correction to Gibbs Free Energy= 0.020077 ---------------------------------------------------- trans-CH3OCCl Symmetry: CS Method: QCISD Basis set: 6-31G* State 1-A'/QCISD=-612.3258588 CCSD(T)/cc-pVDZ=-612.4074924 (single point) 6 -2.228370 0.010724 0.000000 1 -2.674577 -0.423636 0.897309 1 -2.674577 -0.423636 -0.897309 1 -2.309523 1.099663 0.000000 8 -0.824492 -0.369441 0.000000 6 0.000000 0.643508 0.000000 17 1.624990 -0.071897 0.000000 Zero-point correction= 0.047299 Thermal correction to Energy= 0.052215 Thermal correction to Enthalpy= 0.053159 Thermal correction to Gibbs Free Energy= 0.019435 ---------------------------------------------------- cis-CH3OCCl Symmetry: CS Method: B3LYP Basis set: 6-31G* State 1-A'/E(B3LYP)=-613.344175 CCSD(T)/cc-pVDZ=-612.4056731 (single point) CCSD(T)/cc-pVTZ=-612.637271 (single point) CHelpG charges: 6 1.566315 -0.727276 0.000000 * 0.254322 1 1.191920 -1.221899 0.896080 * 0.040716 1 2.652773 -0.661002 0.000000 * -0.029927 1 1.191920 -1.221899 -0.896080 * 0.040716 8 1.106097 0.666250 0.000000 * 0.002488 6 -0.087409 1.122427 0.000000 * -0.175195 17 -1.338755 -0.270359 0.000000 * -0.133120 Zero-point correction= 0.046570 Thermal correction to Energy= 0.051406 Thermal correction to Enthalpy= 0.052350 Thermal correction to Gibbs Free Energy= 0.018663 ---------------------------------------------------- cis-CH3OCCl Symmetry: CS Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM,MeCN)=-613.351057 CHelpG charges: 6 1.585611 -.734305 .000017 * 0.206281 8 1.110596 .664783 -.000040 * 0.046737 6 -.065497 1.127428 .000047 * -0.206838 17 -1.358739 -.269587 -.000006 * -0.190515 1 1.211781 -1.219392 -.899738 * 0.074531 1 2.669506 -.655248 -.000018 * -0.004743 1 1.211833 -1.219391 .899793 * 0.074547 Zero-point correction= 0.046414 Thermal correction to Energy= 0.051363 Thermal correction to Enthalpy= 0.052307 Thermal correction to Gibbs Free Energy= 0.018364 ------------------------------------------------------ cis-CH3OCCl Symmetry: CS Method: MP2 Basis set: 6-31G* State 1-A'/E(MP2)= -612.282412 6 1.456030 -0.883739 0.000000 1 1.030260 -1.331808 0.895592 1 2.541253 -0.935665 0.000000 1 1.030260 -1.331808 -0.895592 8 1.160917 0.552074 0.000000 6 0.000000 1.110688 0.000000 17 -1.330900 -0.128177 0.000000 Zero-point correction= 0.047907 Thermal correction to Energy= 0.052557 Thermal correction to Enthalpy= 0.053502 Thermal correction to Gibbs Free Energy= 0.020260 ---------------------------------------------------- cis-CH3OCCl Symmetry: C1 Method: QCISD Basis set: 6-31G* E(QCISD)=-612.3227157 6 1.547116 -0.718166 0.000039 1 1.174662 -1.214315 0.897653 1 2.634923 -0.654163 -0.000347 1 1.174085 -1.214367 -0.897312 8 1.098380 0.675054 -0.000069 6 -0.120020 1.106753 0.000092 17 -1.313723 -0.273477 -0.000014 Zero-point correction= 0.047397 Thermal correction to Energy= 0.052063 Thermal correction to Enthalpy= 0.053008 Thermal correction to Gibbs Free Energy= 0.019736 ---------------------------------------------------- isomerisation TS for cis- --> trans-CH3OCCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-613.316818 CCSD(T)/cc-pVDZ=-612.3740785 CHelpG charges: 6 -1.978063 -0.461837 0.117470 * 0.071332 8 -0.951584 0.430909 -0.374095 * 0.023826 6 0.035633 0.891937 0.315521 * -0.130013 17 1.525406 -0.236380 -0.015630 * -0.164608 1 -2.735721 -0.498088 -0.662792 * 0.026413 1 -1.536507 -1.448899 0.276790 * 0.093513 1 -2.392424 -0.062422 1.046532 * 0.079537 Low frequencies: -309.3938 160.4049 199.6868 9.3900 7.3130 48.5681 Zero-point correction= 0.045363 Thermal correction to Energy= 0.050010 Thermal correction to Enthalpy= 0.050955 Thermal correction to Gibbs Free Energy= 0.017453 ---------------------------------------------------- isomerisation TS for cis- --> trans-CH3OCCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM/MeCN)=-613.326694 CHelpG charges: 6 -2.188730 -.445747 .088279 * 0.119165 8 -.983289 .325119 -.250194 * 0.237795 6 -.041023 .988298 .165224 * -0.143655 17 1.679954 -.237363 .001799 * -0.425083 1 -2.753136 -.510374 -.836964 * 0.030328 1 -1.843737 -1.420341 .427392 * 0.083692 1 -2.717512 .109635 .859528 * 0.097758 Zero-point correction= 0.044775 Thermal correction to Energy= 0.050024 Thermal correction to Enthalpy= 0.050969 Thermal correction to Gibbs Free Energy= 0.015624 ------------------------------------------------------ isomerisation TS for cis- --> trans-CH3OCCl Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)= -612.2504024 CCSD(T)/cc-pVDZ=-612.3749035 (single point) 6 -1.906510 -0.477642 0.116872 8 -0.941505 0.483000 -0.388392 6 0.064896 0.850470 0.365245 17 1.469824 -0.235821 -0.026271 1 -2.700820 -0.497113 -0.623472 1 -1.424407 -1.453362 0.199374 1 -2.280058 -0.141541 1.085130 Low frequencies: -333.8417 173.1405 213.6707 13.7934 10.3457 40.1259 Zero-point correction= 0.046385 Thermal correction to Energy= 0.050902 Thermal correction to Enthalpy= 0.051846 Thermal correction to Gibbs Free Energy= 0.018661 ---------------------------------------------------- isomerisation TS for cis- --> trans-CH3OCCl Symmetry: C1 Method: QCISD Basis set: 6-31G* E(QCISD)=-612.2927796 CCSD(T)/cc-pVDZ=-612.3752543 (single point) 6 -1.900576 -0.479256 0.117647 8 -0.948331 0.484615 -0.392339 6 0.062294 0.851417 0.369967 17 1.471276 -0.235091 -0.027075 1 -2.703906 -0.508435 -0.617648 1 -1.415238 -1.457208 0.200221 1 -2.276206 -0.147690 1.090738 Low frequencies: -324.2445 172.6814 229.8140 10.5226 3.2312 43.1885 Zero-point correction= 0.045944 Thermal correction to Energy= 0.050434 Thermal correction to Enthalpy= 0.051378 Thermal correction to Gibbs Free Energy= 0.018256 ----------------------------------------------------- fragmentation TS for cis-CH3OCCl --> CH3Cl + CO Symmetry: CS Method: B3LYP Basis set: 6-31G* State 1-A'/E(B3LYP)=-613.2862984 CCSD(T)/cc-pVDZ=-612.346535 (single point) CCSD(T)/cc-pVTZ=-612.572584 (single point) CHelpG charges: 6 -1.501813 -1.006599 0.000000 * 0.121161 8 0.652353 -1.362296 0.000000 * -0.027349 6 1.441390 -0.490018 0.000000 * -0.007089 17 0.000000 1.351012 0.000000 * -0.394454 1 -1.380880 -2.079525 0.000000 * 0.049017 1 -1.737701 -0.504805 0.928108 * 0.129357 1 -1.737701 -0.504805 -0.928108 * 0.129357 Low frequencies: -586.4810 66.2362 189.0983 1.9329 0.2879 2.1873 Zero-point correction= 0.041548 Thermal correction to Energy= 0.047390 Thermal correction to Enthalpy= 0.048334 Thermal correction to Gibbs Free Energy= 0.011906 ---------------------------------------------------- fragmentation TS for cis-CH3OCCl --> CH3Cl + CO Symmetry: CS Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM,MeCN)=-613.303267 CHelpG charges: 6 1.272804 1.375085 .045501 * 0.284668 8 1.333416 -.809134 .195335 * 0.027070 6 .458379 -1.567784 .131433 * -0.001981 17 -1.465936 .193555 -.162760 * -0.655740 1 2.317668 1.162872 -.131471 * 0.062440 1 .624192 1.628849 -.781446 * 0.141041 1 .924627 1.547114 1.055552 * 0.142502 Zero-point correction= 0.044775 Thermal correction to Energy= 0.050024 Thermal correction to Enthalpy= 0.050969 Thermal correction to Gibbs Free Energy= 0.015624 Low frequencies: -271.1105 -36.7865 -15.5807 -4.4282 4.6073 10.3731 ------------------------------------------------------ fragmentation TS for cis-CH3OCCl --> CH3Cl + CO Symmetry: CS Method: MP2 Basis set: 6-31G* State 1-A'/E(MP2)=-612.2087561 6 1.429107 -0.936256 0.000000 8 -0.571096 -1.376131 0.000000 6 -1.450271 -0.581900 0.000000 17 0.000000 1.351147 0.000000 1 1.413555 -2.015244 0.000000 1 1.641097 -0.418135 0.922767 1 1.641097 -0.418135 -0.922767 Low frequencies: -785.4540 141.6560 165.0772 119.5310 2.2500 187.5723 Zero-point correction= 0.042920 Thermal correction to Energy= 0.048532 Thermal correction to Enthalpy= 0.049476 Thermal correction to Gibbs Free Energy= 0.013860 ---------------------------------------------------- isomerisation TS for trans-CH3OCCl --> CH3COCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-613.281203 CCSD(T)/cc-pVDZ=-612.337411 (single point) CCSD(T)/cc-pVTZ=-612.571176 (single point) CHelpG charges: 6 -1.779439 -0.653581 -0.062830 * -0.290312 8 -0.935535 0.923746 -0.216227 * -0.010214 6 -0.266332 0.274280 0.609532 * -0.035627 17 1.506779 -0.149725 -0.070849 * -0.246496 1 -2.245401 -0.433705 -1.023085 * 0.190234 1 -1.174335 -1.558493 -0.116956 * 0.218119 1 -2.436604 -0.576633 0.794081 * 0.174297 Low frequencies: -785.9118 122.9470 254.9302 31.6164 1.2078 0.6295 (The imaginary normal mode corresponds to migration of CH3 group between O and C atoms in COCl) Zero-point correction= 0.043600 Thermal correction to Energy= 0.048500 Thermal correction to Enthalpy= 0.049444 Thermal correction to Gibbs Free Energy= 0.015457 ---------------------------------------------------- isomerisation TS for trans-CH3OCCl --> CH3COCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM,MeCN)=-613.294604 CHelpG charges: 6 1.827373 .787307 -.034678 * -0.067695 8 1.022687 -.934291 -.295542 * 0.005809 6 .396534 -.481551 .622696 * 0.013427 1 1.064257 1.556157 .045287 * 0.205368 17 -1.607072 .165215 -.057472 * -0.531917 1 2.500665 .633584 .798524 * 0.180982 1 2.230369 .641402 -1.030552 * 0.194027 Zero-point correction= 0.042690 Thermal correction to Energy= 0.048245 Thermal correction to Enthalpy= 0.049189 Thermal correction to Gibbs Free Energy= 0.013362 Low frequencies: -616.5393 -40.0261 -3.4663 -1.3240 5.3002 6.8756 ------------------------------------------------------ isomerization TS for trans-CH3OCCl --> CH3COCl Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-612.217480 6 -1.739311 -0.628943 -0.073122 8 -0.919245 0.929136 -0.187135 6 -0.237478 0.205666 0.603849 17 1.470095 -0.139798 -0.074757 1 -2.219146 -0.368946 -1.017554 1 -1.163961 -1.548441 -0.186715 1 -2.393817 -0.599469 0.787857 Low frequencies: -892.3786 143.0782 303.9568 55.4701 2.3763 1.3264 (The imaginary normal mode corresponds to migration of CH3 group between O and C atoms in COCl) Zero-point correction= 0.044773 Thermal correction to Energy= 0.049423 Thermal correction to Enthalpy= 0.050367 Thermal correction to Gibbs Free Energy= 0.016972 ---------------------------------------------------- isomerization TS for trans-CH3OCCl --> CH3COCl Symmetry: C1 Method: QCISD Basis set: 6-31G* E(QCISD)=-612.2525344 6 -1.743740 -0.650689 -0.067574 8 -0.916847 0.939386 -0.201200 6 -0.239264 0.245800 0.605792 17 1.470366 -0.148014 -0.073423 1 -2.209173 -0.414406 -1.025296 1 -1.149181 -1.563540 -0.135716 1 -2.405072 -0.591568 0.789498 Low frequencies: -909.1617 143.8157 275.1354 56.7443 1.6136 0.2471 (The imaginary normal mode corresponds to migration of CH3 group between O and C atoms in COCl) Zero-point correction= 0.044260 Thermal correction to Energy= 0.048994 Thermal correction to Enthalpy= 0.049939 Thermal correction to Gibbs Free Energy= 0.016369 ----------------------------------------------------- CH3 radical (r=1.0828) Symmetry: D3h Method: B3LYP Basis set: 6-31G* E(B3LYP)=-39.8382922 CCSD(T)/cc-pVDZ=-39.716046 (single point) CCSD(T)/cc-pVTZ=-39.760945 (single point) C H 1 1.0828 H 1 1.0828 2 120.0 H 1 1.0828 2 120.0 3 180.0 Zero-point correction= 0.029834 Thermal correction to Energy= 0.032940 Thermal correction to Enthalpy= 0.033885 Thermal correction to Gibbs Free Energy= 0.011699 ---------------------------------------------------- CH3 radical Symmetry: D3h Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM,MeCN)=-39.8388832 C H 1 1.0827 H 1 1.0827 2 120.0 H 1 1.0827 2 120.0 3 180.0 Zero-point correction= .029752 Thermal correction to Energy= .032869 Thermal correction to Enthalpy= .033813 Thermal correction to Gibbs Free Energy= .011611 ---------------------------------------------------- CH3 radical (r=1.0787) Symmetry: D3h Method: MP2 Basis set: 6-31G* E(MP2)=-39.6687503 C H 1 1.0787 H 1 1.0787 2 120.0 H 1 1.0787 2 120.0 3 180.0 Zero-point correction= 0.030526 Thermal correction to Energy= 0.033676 Thermal correction to Enthalpy= 0.034620 Thermal correction to Gibbs Free Energy= 0.012368 ---------------------------------------------------- CH3 radical (r=1.0836) Symmetry: D3h Method: QCISD Basis set: 6-31G* E(QCISD)=-39.6891219 C H 1 1.0836 H 1 1.0836 2 120.0 H 1 1.0836 2 120.0 3 180.0 Zero-point correction= 0.029995 Thermal correction to Energy= 0.033119 Thermal correction to Enthalpy= 0.034064 Thermal correction to Gibbs Free Energy= 0.011845 ---------------------------------------------------- CH3+ (cation), r=1.0946 Symmetry: D3h Method: B3LYP Basis set: 6-31G* E(B3LYP)=-39.4803877 CCSD(T)/cc-pVDZ=-39.367326 (single point) CCSD(T)/cc-pVTZ=-39.404366 (single point) C H 1 1.0946 H 1 1.0946 2 120.0 H 1 1.0946 2 120.0 3 180.0 Zero-point correction= 0.031614 Thermal correction to Energy= 0.034467 Thermal correction to Enthalpy= 0.035411 Thermal correction to Gibbs Free Energy= 0.014214 ---------------------------------------------------- CH3+ (cation) Symmetry: D3h Method: B3LYP Basis set: 6-31G* E(B3LYP/SCIPCM,MeCN)=-39.608341 6 .000000 .000000 .000000 1 .000000 1.083514 .000000 1 .938351 -.541757 .000000 1 -.938351 -.541757 .000000 Zero-point correction= 0.032207 Thermal correction to Energy= 0.035060 Thermal correction to Enthalpy= 0.036004 Thermal correction to Gibbs Free Energy= 0.014836 ------------------------------------------------------ CH3+ (cation), r=1.0889 Symmetry: D3h Method: MP2 Basis set: 6-31G* E(MP2)=-39.3253756 C H 1 1.0889 H 1 1.0889 2 120.0 H 1 1.0889 2 120.0 3 180.0 Zero-point correction= 0.032503 Thermal correction to Energy= 0.035352 Thermal correction to Enthalpy= 0.036297 Thermal correction to Gibbs Free Energy= 0.015118 ---------------------------------------------------- CH3+ (cation), r=1.0929 Symmetry: D3h Method: QCISD Basis set: 6-31G* E(QCISD)=-39.3459645 C H 1 1.0929 H 1 1.0929 2 120.0 H 1 1.0929 2 120.0 3 180.0 Zero-point correction= 0.031976 Thermal correction to Energy= 0.034827 Thermal correction to Enthalpy= 0.035771 Thermal correction to Gibbs Free Energy= 0.014581 ---------------------------------------------------- ******************************************** * * * Calculations on Et-O-C-Cl * * * ******************************************** trans-EtOCCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-652.666125 E(B3LYP/SCIPCM,MeCN)=-652.672248 (single point) CCSD(T)/cc-pVDZ=-651.611325 (single point) CHelpG charges: CHelpG charges(MeCN) 6 1.678918 -0.596140 -0.090284 * 0.485673 * -.176744 8 0.301805 -0.169985 -0.372367 * -0.036831 * -.175450 6 -0.555088 -0.449327 0.554933 * -0.176979 * -.175450 17 -2.140021 0.203368 -0.041983 * -0.098479 * .471552 6 2.547142 0.631159 0.103012 * -0.355689 * -.357786 1 1.972727 -1.178634 -0.966618 * -0.023792 * .000523 1 1.649990 -1.238912 0.792733 * -0.085638 * -.071185 1 3.588140 0.321758 0.247064 * 0.093018 * .110460 1 2.229402 1.196545 0.984543 * 0.135486 * .137859 1 2.499819 1.287715 -0.771050 * 0.063232 * .060902 Zero-point correction= 0.075283 Thermal correction to Energy= 0.081464 Thermal correction to Enthalpy= 0.082408 Thermal correction to Gibbs Free Energy= 0.044935 ---------------------------------------------------- trans-EtOCCl Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-651.4576973 CHelpG charges: 6 1.669645 -0.610508 -0.039706 * 0.472548 8 0.293755 -0.240029 -0.398800 * -0.042822 6 -0.543504 -0.341307 0.592221 * -0.190667 17 -2.105283 0.191543 -0.050394 * -0.068055 6 2.492367 0.651902 0.066893 * -0.357761 1 1.998012 -1.258792 -0.853509 * -0.025508 1 1.626403 -1.169503 0.896193 * -0.081796 1 3.536691 0.394968 0.265626 * 0.092542 1 2.123367 1.274093 0.885014 * 0.132725 1 2.444252 1.222709 -0.862674 * 0.068793 Zero-point correction= 0.077159 Thermal correction to Energy= 0.083195 Thermal correction to Enthalpy= 0.084139 Thermal correction to Gibbs Free Energy= 0.046951 ---------------------------------------------------- cis-EtOCCl Symmetry: CS Method: B3LYP Basis set: 6-31G* State 1-A'/E(B3LYP)=-652.6645035 E(B3LYP/SCIPCM,MeCN)=-652.671115 (single point) CCSD(T)/cc-pVDZ=-651.6094048 (single point) CHelpG charges: CHelpG charges(MeCN) 6 -1.205651 0.092688 0.000000 * 0.476865 * .460540 8 0.000000 0.963001 0.000000 * -0.002271 * .021958 6 1.234243 0.647492 0.000000 * -0.183319 * -.218527 17 1.455923 -1.221755 0.000000 * -0.155706 * -.182668 6 -2.412708 1.003522 0.000000 * -0.530190 * -.550688 1 -1.135915 -0.535998 0.889038 * -0.002236 * .021627 1 -1.135915 -0.535998 -0.889038 * -0.002236 * .021671 1 -3.322658 0.393590 0.000000 * 0.138179 * .155966 1 -2.425756 1.641009 -0.888926 * 0.130457 * .135152 1 -2.425756 1.641009 0.888926 * 0.130457 * .134968 Zero-point correction= 0.075024 Thermal correction to Energy= 0.081157 Thermal correction to Enthalpy= 0.082101 Thermal correction to Gibbs Free Energy= 0.044846 ---------------------------------------------------- cis-EtOCCl Symmetry: CS Method: MP2 Basis set: 6-31G* State 1-A'/E(MP2)=-651.454338 CCSD(T)/cc-pVDZ=-651.6096901 (single point) CHelpG charges: 6 -1.185790 0.075539 0.000000 * 0.514042 8 0.000000 0.961830 0.000000 * -0.022257 6 1.240264 0.620978 0.000000 * -0.207078 17 1.431645 -1.192582 0.000000 * -0.109693 6 -2.390385 0.982400 0.000000 * -0.540104 1 -1.115502 -0.551835 0.889230 * -0.015415 1 -1.115502 -0.551835 -0.889230 * -0.015415 1 -3.299839 0.375272 0.000000 * 0.134092 1 -2.395824 1.617072 -0.887944 * 0.130914 1 -2.395824 1.617072 0.887944 * 0.130914 Zero-point correction= 0.077026 Thermal correction to Energy= 0.082950 Thermal correction to Enthalpy= 0.083895 Thermal correction to Gibbs Free Energy= 0.047153 ---------------------------------------------------- cis'-EtOCCl (ground state for elimination) Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-652.6636579 E(B3LYP/SCIPCM,MeCN)=-652.670165 (single point) CCSD(T)/cc-pVDZ=-651.6085624 (single point) CHelpG charges: CHelpG charges(MeCN) 17 -1.610705 -0.521331 0.059282 * -0.167705 * -.193626 6 -0.770519 1.108672 -0.418385 * -0.147774 * -.184239 8 0.451535 1.129363 -0.065855 * -0.074921 * -.058773 6 1.286561 0.114164 0.630332 * 0.540933 * .551649 6 1.945982 -0.790507 -0.390345 * -0.335279 * -.345236 1 2.006756 0.724634 1.176533 * -0.071764 * -.058026 1 0.637057 -0.421208 1.321861 * -0.021086 * -.006794 1 2.614846 -1.485400 0.129858 * 0.060820 * .073948 1 2.539437 -0.210439 -1.103309 * 0.091110 * .095345 1 1.199475 -1.373840 -0.935510 * 0.125666 * .125753 Zero-point correction= 0.075249 Thermal correction to Energy= 0.081293 Thermal correction to Enthalpy= 0.082237 Thermal correction to Gibbs Free Energy= 0.045203 ---------------------------------------------------- cis'-EtOCCl (ground state for elimination) Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-651.4534955 CCSD(T)/cc-pVDZ=-651.5639236 (single point) CHelpG charges: 17 -1.558963 -0.519479 0.068568 * -0.120431 6 -0.793182 1.071939 -0.424626 * -0.174886 8 0.442197 1.141137 -0.077898 * -0.088071 6 1.271500 0.136082 0.625010 * 0.544350 6 1.884572 -0.801718 -0.388407 * -0.307748 1 2.016534 0.749603 1.130610 * -0.078676 1 0.640061 -0.369796 1.353469 * -0.025385 1 2.563354 -1.489669 0.124004 * 0.047498 1 2.454617 -0.240373 -1.131168 * 0.086059 1 1.112894 -1.385540 -0.891245 * 0.117291 Zero-point correction= 0.077270 Thermal correction to Energy= 0.083091 Thermal correction to Enthalpy= 0.084035 Thermal correction to Gibbs Free Energy= 0.047598 ---------------------------------------------------- Isomerization TS, cis- --> trans-EtOCCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-652.6375837 E(B3LYP/SCIPCM,MeCN)=-652.644963 (single point) CCSD(T)/cc-pVDZ=-651.5779545 (single point) CHelpG charges: CHelpG charges(MeCN) 6 -1.428298 -0.071859 0.564297 * 0.145811 * .154100 8 -0.392120 0.481108 -0.314586 * 0.079399 * .095656 6 0.714380 1.013160 0.061658 * -0.158841 * -.169369 17 2.053673 -0.348433 -0.031592 * -0.186204 * -.231547 6 -2.659259 -0.337524 -0.272560 * -0.451086 * -.491962 1 -1.009816 -0.985018 0.997424 * 0.091035 * .107547 1 -1.607484 0.661499 1.356034 * 0.077463 * .095598 1 -3.439538 -0.762866 0.367900 * 0.149662 * .171941 1 -2.440228 -1.049514 -1.073236 * 0.127419 * .134354 1 -3.039356 0.587731 -0.714741 * 0.125343 * .133681 Low frequences: -291.7760 58.1908 161.4488 10.0176 0.4265 34.8540 (The imaginary normal mode corresponds to a change of the CH2-O-C-Cl dihedral angle) Zero-point correction= 0.073852 Thermal correction to Energy= 0.079764 Thermal correction to Enthalpy= 0.080708 Thermal correction to Gibbs Free Energy= 0.043494 ---------------------------------------------------- Isomerization TS, cis- --> trans-EtOCCl Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-651.4226104 CCSD(T)/cc-pVDZ= (single point) CHelpG charges: 6 -1.360805 -0.130539 0.542195 * 0.145697 8 -0.385877 0.527967 -0.334512 * 0.042787 6 0.741011 0.973242 0.154324 * -0.185035 17 1.989630 -0.344422 -0.051186 * -0.108805 6 -2.626920 -0.300905 -0.257910 * -0.421837 1 -0.922893 -1.085153 0.846213 * 0.082554 1 -1.500457 0.505321 1.420178 * 0.073567 1 -3.378654 -0.799792 0.360086 * 0.140468 1 -2.438994 -0.910005 -1.143530 * 0.115812 1 -3.015403 0.670274 -0.568354 * 0.114792 Low frequences: -318.8404 65.2916 167.7254 14.5293 0.3605 30.4308 (The imaginary normal mode corresponds to CH2-O-C-Cl dihedral angle changing, i.e., to the reaction coordinate) Zero-point correction= 0.075556 Thermal correction to Energy= 0.081306 Thermal correction to Enthalpy= 0.082250 Thermal correction to Gibbs Free Energy= 0.045469 ---------------------------------------------------- fragmentation TS, cis-EtOCCl --> C2H5Cl + CO Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-652.6183515 E(B3LYP/SCIPCM,MeCN)=-652.639640 (single point) CCSD(T)/cc-pVDZ=-651.556560 (single point) CHelpG charges: CHelpG charges(MeCN) 17 1.506214 -0.785139 -0.007538 * -0.496831 * -.663358 6 0.872216 1.572282 -0.299386 * -0.003234 * -.040960 8 -0.235530 1.559765 0.073839 * -0.042782 * -.017551 6 -1.361244 -0.303770 0.745072 * 0.275663 * .437776 6 -1.981997 -0.650364 -0.531625 * -0.119101 * -.225777 1 -1.767164 0.488451 1.363152 * 0.035736 * .042272 1 -0.631952 -0.969564 1.192406 * 0.101340 * .097245 1 -2.732300 -1.431790 -0.289662 * 0.076656 * .139075 1 -1.258486 -1.109859 -1.209224 * 0.112666 * .137758 1 -2.505341 0.183121 -1.003597 * 0.059886 * .093520 Low frequencies: -502.3260 77.3740 92.0743 5.2909 0.5920 2.1935 (The imaginary normal mode corresponds elimination of CO and formation of EtCl) Zero-point correction= 0.069410 Thermal correction to Energy= 0.076838 Thermal correction to Enthalpy= 0.077782 Thermal correction to Gibbs Free Energy= 0.037185 ---------------------------------------------------- fragmentation TS, cis-EtOCCl --> C2H5Cl + CO Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-651.4015364 CHelpG charges: 17 -1.778158 -0.437090 0.000244 * -0.615635 6 1.324065 -1.983682 -0.276642 * 0.030187 8 1.647368 -0.927611 0.063122 * 0.032527 6 0.594505 1.187428 0.712798 * 0.328764 6 0.532571 1.894965 -0.524012 * -0.257237 1 1.457239 1.258773 1.372059 * 0.027280 1 -0.327692 0.611920 0.965713 * 0.054775 1 -0.117851 2.738616 -0.176255 * 0.158233 1 -0.129600 1.359508 -1.215163 * 0.149555 1 1.460806 2.290341 -0.928332 * 0.091551 Low frequencies: -232.0841 59.4661 67.3595 32.8899 4.7657 3.3108 (The imaginary normal mode corresponds elimination of CO and formation of EtCl) Zero-point correction= 0.067793 Thermal correction to Energy= 0.076120 Thermal correction to Enthalpy= 0.077064 Thermal correction to Gibbs Free Energy= 0.033348 ---------------------------------------------------- TS for isomerization trans-EtOCCl --> EtCOCl (concerted) Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-652.6047228 E(B3LYP/SCIPCM,MeCN)=-652.618247 (single point) CCSD(T)/cc-pVDZ=-651.543460 (single point) CHelpG charges: CHelpG charges(MeCN) 6 -1.271314 -0.440693 0.488776 * -0.080650 * -.065206 8 -0.279348 1.143276 0.253467 * -0.034433 * -.028181 6 0.206280 0.387030 -0.585830 * -0.013347 * -.028183 17 2.024046 -0.275271 -0.012590 * -0.331879 * -.415398 6 -2.535400 -0.301823 -0.288268 * -0.061370 * -.088958 1 -0.664602 -1.333654 0.345798 * 0.176002 * .207180 1 -1.300121 -0.150740 1.536824 * 0.148516 * .172572 1 -3.261595 -0.998995 0.157346 * 0.100650 * .134362 1 -2.398804 -0.556973 -1.339870 * 0.035212 * .039544 1 -2.946264 0.706673 -0.201876 * 0.061299 * .072268 Low frequencies: -685.5896 68.5816 97.4432 24.3725 6.4831 0.7516 (The imaginary normal mode corresponds to the reaction coordinate) Zero-point correction= 0.071658 Thermal correction to Energy= 0.078186 Thermal correction to Enthalpy= 0.079131 Thermal correction to Gibbs Free Energy= 0.040627 ---------------------------------------------------- TS for isomerization trans-EtOCCl --> EtCOCl (concerted) Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-651.3877981 CHelpG charges: 6 -1.307950 -0.010310 0.692908 * -0.021962 8 -0.366163 0.940575 -0.564304 * -0.021579 6 0.404753 0.758719 0.411117 * -0.082770 17 1.874932 -0.365003 -0.061203 * -0.225154 6 -2.256742 -0.588726 -0.328437 * 0.095672 1 -0.772240 -0.793151 1.231839 * 0.127958 1 -1.708727 0.760465 1.341624 * 0.092106 1 -2.989201 -1.179611 0.234754 * 0.033870 1 -1.736522 -1.252530 -1.019785 * 0.015108 1 -2.778222 0.187179 -0.887074 * -0.013249 Low frequencies: -854.3632 57.2003 159.6094 60.9022 0.0907 0.7726 (The imaginary normal mode corresponds to the reaction coordinate) Zero-point correction= 0.074012 Thermal correction to Energy= 0.080015 Thermal correction to Enthalpy= 0.080959 Thermal correction to Gibbs Free Energy= 0.043650 ---------------------------------------------------- TS for elimination cis'-EtOCCl --> C2H4 + CO + HCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-652.627595 E(B3LYP/SCIPCM,MeCN)=-652.645356 (single point) CCSD(T)/cc-pVDZ=-651.564051 (single point) CHelpG charges: CHelpG charges(MeCN) 17 -1.750695 -0.419400 0.073248 * -0.457884 * -.592624 6 -0.443590 1.562936 -0.217540 * -0.004384 * -.004515 8 0.707138 1.379602 -0.018173 * -0.019161 * -.022377 6 1.928165 -0.148624 0.262635 * 0.231538 * .340183 6 1.259955 -1.323935 -0.231056 * -0.131444 * -.172296 1 2.672690 0.376629 -0.325576 * 0.027626 * .037554 1 1.962226 0.044737 1.330335 * 0.071759 * .077850 1 1.297633 -2.148991 0.490139 * 0.052862 * .072938 1 1.566183 -1.630145 -1.232236 * 0.060508 * .072763 1 0.138807 -1.091508 -0.246720 * 0.168580 * .190526 Low frequencies: -384.1325 52.6956 176.0195 1.2773 1.1609 2.4397 (The imaginary normal mode corresponds to the reaction coordinate) Zero-point correction= 0.070031 Thermal correction to Energy= 0.076584 Thermal correction to Enthalpy= 0.077528 Thermal correction to Gibbs Free Energy= 0.038911 ---------------------------------------------------- TS for elimination cis'-EtOCCl --> C2H4 + CO + HCl Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-651.4028722 CCSD(T)/cc-pVDZ=-651.5639236 (single point) CHelpG charges: 17 -1.747600 -0.373851 0.070893 * -0.463529 6 -0.366357 1.584241 -0.208027 * -0.005865 8 0.781376 1.328652 -0.021009 * -0.008425 6 1.885718 -0.198501 0.260181 * 0.264545 6 1.177694 -1.335892 -0.232101 * -0.185311 1 2.665758 0.285910 -0.316081 * 0.015192 1 1.927146 -0.016742 1.329480 * 0.061846 1 1.160377 -2.152427 0.494151 * 0.059114 1 1.461289 -1.651241 -1.233276 * 0.067598 1 0.061296 -1.038333 -0.231702 * 0.194835 Low frequencies: -589.0263 43.9442 173.5504 19.2001 1.3739 4.8889 (The imaginary normal mode corresponds to the reaction coordinate) Zero-point correction= 0.071421 Thermal correction to Energy= 0.077797 Thermal correction to Enthalpy= 0.078741 Thermal correction to Gibbs Free Energy= 0.040359 ---------------------------------------------------- C2H5 radical Symmetry: CS Method: B3LYP Basis set: 6-31G* State 2-A'/E(B3LYP)=-79.157867 E(UB3LYP/SCIPCM,MeCN)=-79.158352 (single point) CCSD(T)/cc-pVDZ=-78.916123 CHelpG charges: 6 0.011482 0.795366 0.000000 * -0.321972 6 0.011482 -0.694136 0.000000 * 0.150427 1 0.510933 -1.101704 0.887604 * -0.013493 1 -1.012323 -1.110284 0.000000 * -0.008623 1 0.510933 -1.101704 -0.887604 * -0.013493 1 -0.073661 1.353158 -0.927322 * 0.103577 1 -0.073661 1.353158 0.927322 * 0.103577 Zero-point correction= 0.059658 Thermal correction to Energy= 0.063613 Thermal correction to Enthalpy= 0.064557 Thermal correction to Gibbs Free Energy= 0.035531 ---------------------------------------------------- C2H5 radical Symmetry: CS Method: MP2 Basis set: 6-31G* State 2-A'/E(MP2)=-78.8355987 CHelpG charges: 6 0.014375 0.795298 0.000000 * -0.325887 6 0.014375 -0.695455 0.000000 * 0.156397 1 0.517920 -1.093623 0.885169 * -0.015368 1 -1.006093 -1.105444 0.000000 * -0.009187 1 0.517920 -1.093623 -0.885169 * -0.015368 1 -0.101124 1.346816 -0.924006 * 0.104706 1 -0.101124 1.346816 0.924006 * 0.104706 Zero-point correction= 0.061461 Thermal correction to Energy= 0.065325 Thermal correction to Enthalpy= 0.066270 Thermal correction to Gibbs Free Energy= 0.037522 ---------------------------------------------------- C2H5+ (cation) Symmetry: C2v Method: B3LYP Basis set: 6-31G* State=1-A1/E(B3LYP)=-78.8601098 E(B3LYP/SCIPCM,MeCN)=-79.967536 CCSD(T)/cc-pVDZ=-78.626304 CHelpG charges: 1 0.000000 0.000000 1.060000 * 0.212256 6 0.000000 0.691516 -0.063415 * 0.037263 6 0.000000 -0.691516 -0.063415 * 0.037263 1 -0.936377 1.248990 -0.074754 * 0.178305 1 0.936377 1.248990 -0.074754 * 0.178305 1 -0.936377 -1.248990 -0.074754 * 0.178305 1 0.936377 -1.248990 -0.074754 * 0.178305 Zero-point correction= 0.061050 Thermal correction to Energy= 0.064260 Thermal correction to Enthalpy= 0.065205 Thermal correction to Gibbs Free Energy= 0.039169 ---------------------------------------------------- C2H5+ (cation) Symmetry: C2v Method: MP2 Basis set: 6-31G* State=1-A1/E(MP2)=-78.552310 CHelpG charges: 1 0.000000 0.000000 1.044846 * 0.212927 6 0.000000 0.691018 -0.062521 * 0.034335 6 0.000000 -0.691018 -0.062521 * 0.034335 1 -0.936158 1.245432 -0.073647 * 0.179601 1 0.936158 1.245432 -0.073647 * 0.179601 1 -0.936158 -1.245432 -0.073647 * 0.179601 1 0.936158 -1.245432 -0.073647 * 0.179601 Zero-point correction= 0.062902 Thermal correction to Energy= 0.065983 Thermal correction to Enthalpy= 0.066927 Thermal correction to Gibbs Free Energy= 0.041083 ---------------------------------------------------- ******************************************** * * * Calculations on PhCH2-O-C-Cl * * * ******************************************** trans-PhCH2OCCl Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-844.3996232 E(B3LYP/SCIPCM,MeCN)=-844.406137(single point) CCSD(T)/cc-pVDZ=-842.809607 (single point) CHelpG charges: 6 -0.940553 0.491392 0.394340 * -0.160041 6 -1.877390 1.191191 -0.373292 * -0.085813 6 -3.055138 0.568622 -0.790251 * -0.091966 6 -3.298900 -0.761791 -0.447551 * -0.029859 6 -2.364659 -1.468842 0.314761 * -0.207576 6 -1.192357 -0.844662 0.735806 * 0.129594 6 0.326749 1.156135 0.849164 * 0.339399 1 -1.685885 2.226931 -0.643892 * 0.080036 1 -3.778409 1.121474 -1.383124 * 0.096770 1 -4.214630 -1.248206 -0.772417 * 0.086100 1 -2.552554 -2.504661 0.583160 * 0.121049 1 -0.462570 -1.393073 1.326833 * 0.034417 1 0.577294 0.925011 1.886915 * -0.053297 1 0.302409 2.236632 0.697935 * 0.030968 8 1.468854 0.697062 0.025989 * -0.029251 6 2.300704 -0.073575 0.645396 * -0.150760 17 3.568986 -0.499496 -0.580797 * -0.109769 Zero-point correction= 0.128322 Thermal correction to Energy= 0.137435 Thermal correction to Enthalpy= 0.138379 Thermal correction to Gibbs Free Energy= 0.091690 ---------------------------------------------------- trans-PhCH2OCCl Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-842.589978 6 -0.916596 0.537931 0.381613 6 -1.884624 1.180399 -0.396774 6 -3.038334 0.497449 -0.786150 6 -3.222062 -0.833427 -0.406794 6 -2.252661 -1.481165 0.365021 6 -1.103120 -0.798688 0.759195 6 0.328780 1.252564 0.798015 1 -1.737767 2.216779 -0.695739 1 -3.789837 1.001886 -1.388265 1 -4.119477 -1.366377 -0.711072 1 -2.394819 -2.517748 0.660107 1 -0.341482 -1.298691 1.354934 1 0.592018 1.072130 1.842258 1 0.282116 2.324149 0.594617 8 1.460716 0.771014 -0.022021 6 2.229007 -0.066261 0.611800 17 3.469481 -0.549002 -0.555072 Zero-point correction= 0.128990 Thermal correction to Energy= 0.138153 Thermal correction to Enthalpy= 0.139098 Thermal correction to Gibbs Free Energy= 0.092585 ---------------------------------------------------- cis-PhCH2OCCl Symmetry: CS Method: B3LYP Basis set: 6-31G* State 1-A'/E(B3LYP)=-844.3983816 E(B3LYP/SCIPCM,MeCN)=-844.4063404(single point) CCSD(T)/cc-pVDZ=-842.807455 (single point) CHelpG charges: 6 0.720614 -0.496289 0.000000 * -0.227766 6 2.037799 -2.968292 0.000000 * -0.030534 1 2.550749 -3.926126 0.000000 * 0.078640 6 0.000000 0.811573 0.000000 * 0.398991 8 -1.483217 0.530121 0.000000 * -0.010293 1 0.184859 1.412389 0.890610 * 0.015792 1 0.184859 1.412389 -0.890610 * 0.015792 6 1.054394 -1.121344 -1.208579 * -0.050972 6 1.054394 -1.121344 1.208579 * -0.050972 6 1.709991 -2.351733 1.209436 * -0.084861 6 1.709991 -2.351733 -1.209436 * -0.084861 1 0.799011 -0.641285 -2.150280 * 0.099446 1 0.799011 -0.641285 2.150280 * 0.099446 1 1.966584 -2.827672 2.151633 * 0.082433 1 1.966584 -2.827672 -2.151633 * 0.082433 6 -2.457227 1.345251 0.000000 * -0.164856 17 -1.856804 3.136575 0.000000 * -0.167860 Zero-point correction= 0.127829 Thermal correction to Energy= 0.137006 Thermal correction to Enthalpy= 0.137951 Thermal correction to Gibbs Free Energy= 0.091089 ---------------------------------------------------- cis-PhCH2OCCl Symmetry: CS Method: MP2 Basis set: 6-31G* State 1-A'/E(MP2)=-842.586382 CCSD(T)/cc-pVDZ=-842.8080979 (single point) 6 0.717667 -0.474276 0.000000 6 2.006848 -2.957029 0.000000 1 2.511668 -3.919826 0.000000 6 0.000000 0.829793 0.000000 8 -1.462165 0.520846 0.000000 1 0.192535 1.428973 0.891615 1 0.192535 1.428973 -0.891615 6 1.039801 -1.100906 -1.210003 6 1.039801 -1.100906 1.210003 6 1.685123 -2.337227 1.210002 6 1.685123 -2.337227 -1.210002 1 0.787906 -0.616796 -2.151926 1 0.787906 -0.616796 2.151926 1 1.936417 -2.817622 2.152144 1 1.936417 -2.817622 -2.152144 6 -2.434022 1.361964 0.000000 17 -1.828830 3.085813 0.000000 Zero-point correction= 0.128634 Thermal correction to Energy= 0.137813 Thermal correction to Enthalpy= 0.138757 Thermal correction to Gibbs Free Energy= 0.092068 ---------------------------------------------------- isomerization TS for cis- --> trans-PhCH2OCCl rearrangement Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-844.3710068 E(B3LYP/SCIPCM,MeCN)=-844.3797379(single point) CCSD(T)/cc-pVDZ=-842.775406 (single point) CHelpG charges: 6 -0.472101 -0.509135 0.840057 * 0.176715 8 -1.352849 -0.515498 -0.357265 * 0.042878 6 -2.550548 -0.968832 -0.386660 * -0.145526 17 -3.730309 0.529744 -0.141041 * -0.200106 6 0.924845 -0.187426 0.416483 * -0.151231 1 -0.896186 0.244766 1.507776 * 0.084414 1 -0.557156 -1.500121 1.292496 * 0.068009 6 1.822425 -1.215573 0.103382 * -0.027643 6 1.343466 1.145745 0.319418 * -0.013494 6 2.643597 1.446354 -0.083248 * -0.091701 6 3.123501 -0.915775 -0.298243 * -0.089105 6 3.534460 0.415548 -0.391677 * -0.056569 1 0.647265 1.946241 0.557065 * 0.060394 1 1.499927 -2.251541 0.174848 * 0.065964 1 2.962186 2.482377 -0.154470 * 0.096218 1 3.815327 -1.718693 -0.536241 * 0.093987 1 4.548813 0.649862 -0.702730 * 0.086795 Low frequencies: -282.8254 23.9247 33.1104 13.1414 1.2164 0.1197 (The imaginary normal mode corresponds to the reaction coordinate) Zero-point correction= 0.126713 Thermal correction to Energy= 0.135627 Thermal correction to Enthalpy= 0.136571 Thermal correction to Gibbs Free Energy= 0.089839 ---------------------------------------------------- isomerization TS for cis- --> trans-PhCH2OCCl rearrangement Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-842.554070 6 -0.513884 -0.511172 0.805220 8 -1.325488 -0.516715 -0.430114 6 -2.561465 -0.936198 -0.380224 17 -3.629865 0.527251 -0.115984 6 0.888867 -0.191825 0.417109 1 -0.949550 0.247045 1.462879 1 -0.606809 -1.499805 1.263715 6 1.789420 -1.221379 0.121407 6 1.297064 1.142621 0.306350 6 2.601542 1.444239 -0.083467 6 3.094442 -0.918651 -0.267167 6 3.500628 0.413929 -0.370978 1 0.591716 1.942022 0.526053 1 1.468263 -2.258483 0.199301 1 2.916940 2.481286 -0.164794 1 3.793220 -1.720538 -0.491312 1 4.518141 0.649542 -0.672712 Low frequencies: -311.3722 15.3001 35.2302 18.3310 0.9234 0.0547 (The imaginary normal mode corresponds to the reaction coordinate) Zero-point correction= 0.127202 Thermal correction to Energy= 0.136178 Thermal correction to Enthalpy= 0.137122 Thermal correction to Gibbs Free Energy= 0.090032 ---------------------------------------------------- fragmentation TS for cis-PhCH2OCCl --> PhCH2Cl + CO Symmetry: C1 Method: B3LYP Basis set: 6-31G* E(B3LYP)=-844.384735 E(B3LYP/SCIPCM,MeCN)=-844.4064569(single point) CCSD(T)/cc-pVDZ=-842.781890 (single point) CHelpG charges: 6 -0.764927 0.458600 -0.505779 * 0.114262 6 -0.729458 -0.937824 -0.224027 * 0.053807 6 -1.967187 1.187913 -0.281056 * -0.080364 6 -3.096289 0.538795 0.183479 * -0.125069 6 -3.046669 -0.841081 0.444248 * 0.042059 6 -1.870203 -1.573781 0.242720 * -0.174964 6 0.378485 1.093307 -1.015971 * -0.114257 8 1.676098 1.563799 0.700709 * -0.046721 6 2.560737 0.916174 1.116856 * -0.000800 17 2.811387 -1.065080 -0.208398 * -0.509529 1 0.348974 2.145105 -1.282768 * 0.128382 1 1.237915 0.503940 -1.326467 * 0.183590 1 0.211873 -1.467371 -0.352342 * 0.095869 1 -1.987401 2.254161 -0.489739 * 0.105307 1 -1.848379 -2.636882 0.461166 * 0.126157 1 -4.017103 1.089401 0.349169 * 0.112678 1 -3.935171 -1.345011 0.815260 * 0.089593 Low frequencies: -91.8997 58.2556 72.0535 86.2522 2.5341 0.2790 (The imaginary normal mode corresponds elimination of CO and formation of PhCH2Cl) Zero-point correction= 0.124860 Thermal correction to Energy= 0.134582 Thermal correction to Enthalpy= 0.135526 Thermal correction to Gibbs Free Energy= 0.088443 ---------------------------------------------------- fragmentation TS for cis-PhCH2OCCl --> PhCH2Cl + CO Symmetry: C1 Method: MP2 Basis set: 6-31G* E(MP2)=-842.559873 CCSD(T)/cc-pVDZ=-842.7829601 (single point) 6 0.672036 -0.947261 -0.149510 6 1.844709 -1.568738 0.264091 6 3.026305 -0.828575 0.386240 6 3.052979 0.545011 0.100837 6 1.893075 1.184667 -0.309277 6 0.699518 0.436830 -0.446199 1 -0.278341 -1.474931 -0.225426 1 1.841672 -2.629763 0.496729 1 3.938681 -1.323464 0.711195 1 3.979561 1.102645 0.203373 1 1.892671 2.249135 -0.535526 6 -0.484096 1.053109 -0.921917 8 -1.520838 1.549393 0.651519 6 -2.433989 0.959192 1.135615 1 -0.442005 2.077585 -1.283065 1 -1.322833 0.424263 -1.228614 17 -2.768584 -1.048589 -0.218242 Low frequencies: -330.8686 63.3669 80.6646 532.3796 3.2330 0.0817 (The imaginary normal mode corresponds elimination of CO and formation of PhCH2Cl) Zero-point correction= 0.125873 Thermal correction to Energy= 0.135451 Thermal correction to Enthalpy= 0.136395 Thermal correction to Gibbs Free Energy= 0.089954 ---------------------------------------------------- neutral complex PhCH2::Cl Symmetry: CS Method: B3LYP Basis set: 6-31G* State=1-A'\E(B3LYP)=-731.0756183 CCSD(T)/cc-pVDZ=-729.731730 CHelpG charges: 6 0.000000 0.719648 0.000000 * 0.099599 6 -0.849752 1.811319 0.000000 * -0.184197 6 -2.239136 1.614894 0.000000 * 0.080878 6 -2.799373 0.323348 0.000000 * -0.122648 6 -1.968543 -0.778396 0.000000 * -0.059561 6 -0.546933 -0.606142 0.000000 * 0.067181 1 1.086891 0.816078 0.000000 * 0.085087 1 -0.444762 2.818360 0.000000 * 0.134564 1 -2.900056 2.477810 0.000000 * 0.088735 1 -3.878005 0.201680 0.000000 * 0.114287 1 -2.377827 -1.784993 0.000000 * 0.108638 6 0.318130 -1.693147 0.000000 * 0.037070 1 -0.088027 -2.703919 0.000000 * 0.103657 1 1.410111 -1.539367 0.000000 * 0.112960 17 3.276783 -0.507929 0.000000 * -0.666251 Low frequencies: -475.1078 87.5399 87.5796 1.7168 4.7190 2.5796 (The imaginary normal mode corresponds to -CH2 group rotation; IRC leads to PhCH2Cl) Zero-point correction= 0.116118 Thermal correction to Energy= 0.123491 Thermal correction to Enthalpy= 0.124436 Thermal correction to Gibbs Free Energy= 0.083060 ---------------------------------------------------- B3LYP/6-31G* Stable Guess=Mix shows RHF <--> UHF wave- function instability, which means the complex has partially triplet character. Optimization of the wavefunction at the above geometry gives E(B3LYP)=-731.0779497 [UB3LYP/6-31G* POP=REG GUESS=MIX SCF=(QC,NOSYM,CYCLES=900,DIRECT)], S2=0.288838 Optimization of geometry with an optimized wavefunction gives the following results: ------------------------------------------------------ neutral complex PhCH2::Cl Symmetry: C1 Method: E(B3LYP/SCIPCM/MeCN)=-731.1095376 Basis set: 6-31G* 6 .165024 -.652702 .006437 6 1.209134 -1.554447 .003863 6 2.532682 -1.079007 -.001730 6 2.836083 .298405 -.005410 6 1.809773 1.216107 -.003863 6 .446841 .758627 .002754 1 -.880758 -.960168 .010492 1 1.019153 -2.621928 .006165 1 3.349354 -1.794798 -.003355 1 3.870531 .622595 -.009525 1 2.008904 2.282851 -.006718 6 -.604130 1.646705 .007059 1 -.426784 2.719046 .002787 1 -1.635028 1.271344 .014185 17 -3.392813 -.313003 -.004041 Zero-point correction= 0.117862 Thermal correction to Energy= 0.125787 Thermal correction to Enthalpy= 0.126731 Thermal correction to Gibbs Free Energy= 0.083227 ---------------------------------------------------- neutral complex PhCH2::Cl Symmetry: CS Method: UB3LYP pop=reg guess=mix scf=(qc,NoSym, Cycles=900,direct) Basis set: 6-31G* State=1-A'\E(B3LYP)= -731.078723 CHelpG charges: 6 0.000000 0.712786 0.000000 * 0.057566 6 -0.787235 1.850218 0.000000 * -0.149768 6 -2.186154 1.736335 0.000000 * 0.047246 6 -2.811993 0.476498 0.000000 * -0.115864 6 -2.042875 -0.670190 0.000000 * -0.075734 6 -0.613766 -0.582544 0.000000 * 0.095435 1 1.087128 0.763003 0.000000 * 0.088010 1 -0.324172 2.832147 0.000000 * 0.127083 1 -2.797463 2.634744 0.000000 * 0.093822 1 -3.895744 0.410940 0.000000 * 0.113861 1 -2.509605 -1.651530 0.000000 * 0.108943 6 0.182458 -1.723160 0.000000 * -0.036475 1 -0.278056 -2.708786 0.000000 * 0.117746 1 1.271809 -1.647307 0.000000 * 0.123260 17 3.353147 -0.672521 0.000000 * -0.595132 Low frequencies: -304.0156 75.4259 108.5636 4.8835 2.6694 0.2228 (The imaginary normal mode corresponds to the -CH2 group rotation) Zero-point correction= 0.116233 Thermal correction to Energy= 0.123637 Thermal correction to Enthalpy= 0.124581 Thermal correction to Gibbs Free Energy= 0.083049 ---------------------------------------------------- neutral PhCH2::Cl complex Symmetry: CS Method: MP2 Basis set: 6-31G* State=1-A'/MP2=-729.5478134 6 0.000000 0.641243 0.000000 6 -0.922181 1.677920 0.000000 6 -2.292240 1.390833 0.000000 6 -2.779161 0.066319 0.000000 6 -1.887866 -0.985742 0.000000 6 -0.485038 -0.706281 0.000000 1 1.091087 0.780875 0.000000 1 -0.582069 2.709149 0.000000 1 -3.007175 2.211424 0.000000 1 -3.849985 -0.114119 0.000000 1 -2.230289 -2.018518 0.000000 6 0.460876 -1.715637 0.000000 1 0.146847 -2.759560 0.000000 1 1.536802 -1.443495 0.000000 17 3.195791 -0.092805 0.000000 ---------------------------------------------------- PhCH2Cl Symmetry: CS Method: B3LYP Basis set: 6-31G* State=1-A'/E(B3LYP)=-731.160253 E(B3LYP/SCIPCM,MeCN)=-731.1649717 (single point) CCSD(T)/cc-pVDZ=-729.840251 (single point) CHelpG charges: 6 0.000000 0.445066 0.000000 * 0.127492 6 2.646960 -0.483476 0.000000 * -0.067224 1 3.673086 -0.840916 0.000000 * 0.088226 6 -1.412463 0.947906 0.000000 * -0.091814 17 -2.646687 -0.417426 0.000000 * -0.202583 1 -1.638218 1.536850 0.889835 * 0.098965 1 -1.638218 1.536850 -0.889835 * 0.098965 6 0.670566 0.209391 -1.207195 * -0.136552 6 0.670566 0.209391 1.207195 * -0.136552 6 1.986398 -0.251919 1.208293 * -0.095339 6 1.986398 -0.251919 -1.208293 * -0.095339 1 0.156642 0.386728 -2.149050 * 0.110071 1 0.156642 0.386728 2.149050 * 0.110071 1 2.496605 -0.428321 2.151304 * 0.095806 1 2.496605 -0.428321 -2.151304 * 0.095806 Zero-point correction= 0.120129 Thermal correction to Energy= 0.127058 Thermal correction to Enthalpy= 0.128003 Thermal correction to Gibbs Free Energy= 0.087390 ---------------------------------------------------- PhCH2Cl Symmetry: CS Method: MP2 Basis set: 6-31G* State=1-A'/E(MP2)=-729.656448 6 0.000000 0.450343 0.000000 6 2.618164 -0.549443 0.000000 1 3.634544 -0.935438 0.000000 6 -1.401393 0.975141 0.000000 17 -2.615555 -0.353761 0.000000 1 -1.600126 1.577421 0.888095 1 -1.600126 1.577421 -0.888095 6 0.660534 0.196614 -1.207891 6 0.660534 0.196614 1.207891 6 1.963713 -0.300730 1.208723 6 1.963713 -0.300730 -1.208723 1 0.149363 0.385583 -2.150443 1 0.149363 0.385583 2.150443 1 2.469908 -0.491744 2.151834 1 2.469908 -0.491744 -2.151834 ---------------------------------------------------- PhCH2 (benzyl radical) Symmetry: C2v Method: B3LYP Basis set: 6-31G* State=2-B1/E(B3LYP)=-270.9151433 E(UB3LYP/SCIPCM,MeCN)=-270.9175582(single point) CCSD(T)cc-pVDZ=-270.131915 6 0.00 0.995266 0.000000 6 0.00 -1.839775 0.000000 6 0.00 0.252015 1.218112 6 0.00 0.252015 -1.218112 6 0.00 -1.133872 1.211957 6 0.00 -1.133872 -1.211957 6 0.00 2.401815 0.000000 1 0.00 0.793920 -2.160777 1 0.00 0.793920 2.160777 1 0.00 -1.676705 -2.153794 1 0.00 -1.676705 2.153794 1 0.00 -2.926079 0.000000 1 0.00 2.965047 -0.927739 1 0.00 2.965047 0.927739 Zero-point correction= 0.114952 Thermal correction to Energy= 0.120620 Thermal correction to Enthalpy= 0.121564 Thermal correction to Gibbs Free Energy= 0.085938 ---------------------------------------------------- PhCH2+ (benzyl cation) Symmetry: C2v Method: B3LYP Basis set: 6-31G* State=1-A1/E(B3LYP)=-270.662271 CCSD(T)cc-pVDZ=-269.881783 6 0.000000 1.246316 0.254346 6 0.000000 1.235808 -1.121523 6 0.000000 0.000000 -1.802563 6 0.000000 -1.235808 -1.121523 6 0.000000 -1.246316 0.254346 6 0.000000 0.000000 0.982919 6 0.000000 0.000000 2.353330 1 0.000000 2.180971 0.807786 1 0.000000 2.163267 -1.684141 1 0.000000 0.000000 -2.889633 1 0.000000 -2.163267 -1.684141 1 0.000000 -2.180971 0.807786 1 0.000000 -0.926453 2.923173 1 0.000000 0.926453 2.923173 Zero-point correction= 0.117619 Thermal correction to Energy= 0.123253 Thermal correction to Enthalpy= 0.124197 Thermal correction to Gibbs Free Energy= 0.089137 ---------------------------------------------------- PhCH2+ (benzyl cation) Symmetry: C2v Method: MP2 Basis set: 6-31G* State=1-A1/E(MP2)=-269.742568 6 0.000000 1.246699 0.259148 6 0.000000 1.233783 -1.120465 6 0.000000 0.000000 -1.800946 6 0.000000 -1.233783 -1.120465 6 0.000000 -1.246699 0.259148 6 0.000000 0.000000 0.974253 6 0.000000 0.000000 2.347984 1 0.000000 2.181889 0.815144 1 0.000000 2.162259 -1.683099 1 0.000000 0.000000 -2.889178 1 0.000000 -2.162259 -1.683099 1 0.000000 -2.181889 0.815144 1 0.000000 -0.927571 2.916580 1 0.000000 0.927571 2.916580 Zero-point correction= 0.117867 Thermal correction to Energy= 0.123677 Thermal correction to Enthalpy= 0.124621 Thermal correction to Gibbs Free Energy= 0.089249 ---------------------------------------------------- ******************************************** * * * Calculations on small molecules * * * ******************************************** COCl radical Symmetry: CS Method: B3LYP Basis set: 6-31G* State 2-A'/E(B3LYP)=-573.463961 CCSD(T)/cc-pVDZ=-572.652827 CCSD(T)/cc-pVTZ=-572.833870 CCSD(T)/cc-pVQZ= C O 1 r1 Cl 1 r2 2 a Variables: r1 1.1636 r2 1.8401 a 128.8265 Zero-point correction= 0.006573 Thermal correction to Energy= 0.009955 Thermal correction to Enthalpy= 0.010900 Thermal correction to Gibbs Free Energy= -0.019127 ---------------------------------------------------- COCl radical Symmetry: CS Method: MP2 Basis set: 6-31G* State 2-A'/E(MP2)=-572.576357 C O 1 r1 Cl 1 r2 2 a Variables: r1 1.1753 r2 1.7966 a 128.8778 Zero-point correction= 0.006888 Thermal correction to Energy= 0.010186 Thermal correction to Enthalpy= 0.011130 Thermal correction to Gibbs Free Energy= -0.018722 ---------------------------------------------------- CO molecule Symmetry: C*v Method: B3LYP Basis set: 6-31G* State=1-SG/E(B3LYP)=-113.3102898 CCSD(T)/cc-pVDZ=-113.054881 CCSD(T)/cc-pVTZ=-113.155568 C O 1 r Variables: r=1.13802 Zero-point correction= 0.005030 Thermal correction to Energy= 0.007391 Thermal correction to Enthalpy= 0.008335 Thermal correction to Gibbs Free Energy= -0.014108 ---------------------------------------------------- CO molecule Symmetry: C*v Method: MP2 Basis set: 6-31G* State=1-SG/E(MP2)=-113.0212153 C O 1 r Variables: r=1.1512 Zero-point correction= 0.004828 Thermal correction to Energy= 0.007189 Thermal correction to Enthalpy= 0.008133 Thermal correction to Gibbs Free Energy= -0.014333 ----------------------------------------------------