Ground and excited state
CASPT
2 geometry
optimisations of small organic molecules
Christopher S. Page
∗and Massimo Olivucci
†Dipartimento di Chimica, Università di Siena, via Aldo Moro, I-53100 Siena, Italy
and
Centro per lo Studio dei Sistemi Complessi, via Tommaso Pendola 37, I-53100 Siena, Italy
22
ndMay, 2002
Supporting Information
CASSCF
and
CASPT2 Geometries in Cartesian Coordinates (a.u)
acetone s0 casscf
O1 .000000 .000000 2.463395
C2 .000000 .000000 .183303
C3 .000000 2.440833 -1.307510
H4 .000000 4.035849 -.029576
H5 1.652656 2.543224 -2.520666
caspt2
O1 .000000 .000000 2.494606
C2 .000000 .000000 .178674
C3 .000000 2.429733 -1.321587
H4 .000000 4.036178 -.032478
H5 1.664673 2.518402 -2.545462
acetone s1 casscf
O1 .000000 .000000 2.566670
C2 .000000 .000000 -.027355
C3 .000000 2.523299 -1.289199
H4 .000000 4.022385 .107010
H5 1.656991 2.776774 -2.480663
∗Present address: Biomolecular Modelling Laboratory, Imperial Cancer Research Fund, 44 Lincoln’s Inn
Fields, London GB-WC2A 3PX.
caspt2
O1 .000000 .000000 2.568343
C2 .000000 .000000 -.016225
C3 .000000 2.508449 -1.292648
H4 .000000 4.028154 .103694
H5 1.670296 2.750041 -2.498242
acrolein s0 casscf
C1 -.150417 -1.337727 .000000
C2 .109098 1.440515 .000000
C3 2.373995 2.579665 .000000
O4 -2.168230 -2.402359 .000000
H5 1.601406 -2.424983 .000000
H6 4.103243 1.508171 .000000
H7 2.555810 4.601175 .000000
H8 -1.623863 2.503300 .000000
caspt2
C1 -.142532 -1.314221 .000000
C2 .098278 1.451518 .000000
C3 2.378904 2.572886 .000000
O4 -2.174371 -2.425969 .000000
H5 1.658649 -2.374452 .000000
H6 4.109821 1.473847 .000000
H7 2.589379 4.607437 .000000
H8 -1.647283 2.525369 .000000
acrolein s1 casscf
C1 -.064053 -1.245062 .000000
C2 .147704 1.343071 .000000
C3 2.457430 2.636011 .000000
O4 -2.326319 -2.440957 .000000
H5 1.497905 -2.542097 .000000
H6 4.228378 1.643744 .000000
H7 2.514107 4.660954 .000000
H8 -1.576254 2.423630 .000000
caspt2
C1 -.082733 -1.230798 .000000
C2 .137919 1.374134 .000000
C3 2.449635 2.632746 .000000
O4 -2.300506 -2.475500 .000000
H5 1.523350 -2.522654 .000000
H6 4.225607 1.614122 .000000
H7 2.535206 4.673595 .000000
acrolein ci casscf
C1 -1.073559 -.528982 .028856
C2 .971617 .830372 -.012466
C3 3.558307 -.253492 -.004646
O4 -3.666840 .088893 -.010633
H5 -1.276950 -2.563782 .104406
H6 4.599907 -.449332 1.724630
H7 4.456861 -.846330 -1.723042
H8 .816710 2.860914 -.091390
caspt2
C1 -.960846 -.471366 .031390
C2 1.150862 .818449 -.022240
C3 3.722307 -.250491 -.010432
O4 -3.511016 -.015125 .000963
H5 -1.311680 -2.543925 .124384
H6 4.771175 -.463248 1.751500
H7 4.684110 -.776549 -1.753628
H8 .995391 2.873674 -.122267
cis butadiene s0 casscf
C1 2.920411 -.983810 .000000
C2 1.394798 1.048184 .000000
H1 4.939747 -.769932 .000000
H2 2.211726 -2.887642 .000000
H3 2.259550 2.891089 .000000
caspt2
C1 2.911674 -.989760 .000000
C2 1.387211 1.055495 .000000
H1 4.950157 -.788021 .000000
H2 2.189050 -2.908502 .000000
H3 2.266313 2.913827 .000000
cis butadiene 1bu casscf
C1 2.710420 -1.088247 .000000
C2 1.313850 1.172021 .000000
H1 4.736579 -1.029641 .000000
H2 1.847878 -2.909875 .000000
H3 2.308606 2.942034 .000000
caspt2
C1 2.743297 -1.095930 .000000
C2 1.321818 1.181580 .000000
H2 1.844147 -2.940346 .000000
H3 2.320177 2.974242 .000000
cis butadiene 2a1 casscf
C1 2.962431 -1.119701 .000000
C2 1.335996 1.197329 .000000
H1 4.977815 -.933238 .000000
H2 2.169286 -2.979802 .000000
H3 2.287954 2.988739 .000000
caspt2
C1 2.923740 -1.131525 .000000
C2 1.318037 1.211900 .000000
H1 4.960577 -.972141 .000000
H2 2.101278 -2.999348 .000000
H3 2.295478 3.014474 .000000
cis butadiene s0s1 casscf
C1 -1.700983 -1.058931 -.722537
C2 .729916 -1.345880 .285382
C3 -1.869982 1.497486 .296338
C4 2.738694 .510912 -.207229
H5 -3.125859 -2.434201 -.271580
H6 1.170439 -2.848985 1.600825
H7 -1.385579 3.164880 -.744930
H8 -2.755521 1.803467 2.103781
H9 2.662252 1.681031 -1.858905
H10 4.048399 1.012282 1.259085
caspt2
C1 -1.678733 -1.078648 -.680923
C2 .803942 -1.303549 .262657
C3 -1.839200 1.505604 .208882
C4 2.621099 .673423 .021794
H5 -3.055278 -2.466982 -.061931
H6 1.295024 -2.859016 1.532883
H7 -1.378719 3.131566 -.946013
H8 -2.624571 1.944447 2.059514
H9 2.578775 1.976227 -1.550053
H10 4.290809 .692851 1.199199
cis butadiene c2 ci casscf
C1 2.355724 -.985371 -.098564
C2 1.340350 1.178867 .070473
C3 -2.353353 -.989961 .094975
C4 -1.337825 1.177652 -.055198
H6 1.332755 -2.653056 -.602794
H7 2.405003 2.888844 .352864
H8 -1.347671 -2.653116 .642157
H9 -4.381937 -1.168323 -.024203
H10 -2.400148 2.887170 -.350077
caspt2
C1 2.749239 -1.125977 -.113769
C2 1.314074 1.218031 .045480
C3 -2.748185 -1.134422 .095534
C4 -1.313535 1.210551 -.029867
H5 4.790219 -1.125135 -.040829
H6 1.796327 -2.851012 -.667903
H7 2.332687 2.978170 .293092
H8 -1.815479 -2.845569 .725168
H9 -4.788218 -1.129398 -.001106
H10 -2.334507 2.970432 -.277206
cis butadiene c2v ci casscf
C1 -.010285 -1.002976 2.309331
C2 -.010285 1.178031 1.341708
C3 -.010285 1.178031 -1.341708
C4 -.010285 -1.002976 -2.309331
H5 -.811020 -2.688640 1.551348
H6 .581624 -1.245805 4.254834
H7 .352820 2.884115 2.415038
H8 .352820 2.884115 -2.415038
H9 .581624 -1.245805 -4.254834
H10 -.811020 -2.688640 -1.551348
caspt2
C1 .094084 -1.131462 2.560416
C2 -.099647 1.218978 1.320258
C3 -.096138 1.220456 -1.321829
C4 .096358 -1.127363 -2.559952
H5 -.888463 -2.796180 1.883911
H6 .908628 -1.262553 4.437484
H7 .003764 2.980478 2.378311
H8 .009742 2.983000 -2.377381
H9 .898866 -1.260915 -4.441267
H10 -.868932 -2.794301 -1.867874
trans butadiene s0 casscf
C1 1.146630 3.316335 .000000
C2 1.146630 .776124 .000000
H3 -.584605 4.383971 .000000
H5 2.922720 -.221382 .000000
caspt2
C1 1.141878 3.306903 .000000
C2 1.143774 .760832 .000000
H3 -.611323 4.371726 .000000
H4 2.881873 4.385713 .000000
H5 2.931814 -.257111 .000000
trans butadiene 1bu casscf
C1 1.140667 3.417979 .000000
C2 1.085140 .751743 .000000
H3 -.570481 4.506030 .000000
H4 2.903610 4.411746 .000000
H5 2.877713 -.214093 .000000
caspt2
C1 1.145082 3.409604 .000000
C2 1.104945 .725546 .000000
H3 -.619538 4.466053 .000000
H4 2.921274 4.434171 .000000
H5 2.909279 -.270746 .000000
trans butadiene 2ag casscf
C1 1.174393 3.550698 .000000
C2 1.130606 .719523 .000000
H3 -.552005 4.610846 .000000
H4 2.934152 4.549811 .000000
H5 2.916633 -.246631 .000000
caspt2
C1 1.168880 3.540213 .000000
C2 1.119704 .706523 .000000
H3 -.575321 4.606179 .000000
H4 2.943687 4.548890 .000000
H5 2.925575 -.268967 .000000
trans butadiene ci casscf
C1 -.861170 .836127 -.534076
C2 1.121907 -.917049 -1.043891
C3 -3.227881 -.038868 .592502
C4 3.093144 .137323 .591917
H5 -.567155 2.806035 -.933539
H6 .726563 -2.911489 -.991534
H7 -3.150073 -1.328961 2.160005
H8 -4.897313 -.150210 -.570755
H10 3.282927 -.499052 2.515663
caspt2
C1 -.852333 .823718 -.437676
C2 1.072014 -.924197 -.951385
C3 -3.242637 -.046664 .600972
C4 3.090107 .153418 .588860
H5 -.538649 2.819652 -.822620
H6 .642583 -2.934176 -.949336
H7 -3.242718 -1.384466 2.159057
H8 -4.875385 -.133110 -.653978
H9 3.836863 2.003300 .101302
H10 3.377740 -.445911 2.537755
diazomethane s0 casscf
C1 -2.304661 .000000 .000000
N2 .146252 .000000 .000000
N3 2.294853 .000000 .000000
H4 -3.238182 1.787293 .000000
caspt2
C1 -2.323634 .000000 .000000
N2 .136623 .000000 .000000
N3 2.325452 .000000 .000000
H4 -3.270907 1.802079 .000000
diazomethane s1 casscf
C1 -2.400817 .000000 .000000
N2 .152387 .000000 .000000
N3 2.393802 .000000 .000000
H4 -3.395768 1.767769 .000000
caspt2
C1 -2.386575 .000000 .000000
N2 .121282 .000000 .000000
N3 2.417026 .000000 .000000
H4 -3.425800 1.778626 .000000
diazomethane ci casscf
C1 1.776573 -1.054988 .000000
N2 -.000000 .934805 .000000
N3 -2.217733 .471710 .000000
H4 1.136868 -2.974036 .000000
H5 3.727819 -.541643 .000000
C1 1.900700 -1.136332 .000000
N2 .127005 .861681 .000000
N3 -2.123960 .378247 .000000
H4 1.245230 -3.068715 .000000
H5 3.869833 -.629170 .000000
propenoic acid s0 casscf
O1 2.318980 1.251523 .000000
O2 -1.657993 2.724084 .000000
C3 -.018716 1.035968 .000000
C4 -1.082014 -1.647787 .000000
C5 .327172 -3.760006 .000000
H6 -.518205 -5.616427 .000000
H7 2.355725 -3.641883 .000000
H8 -3.117226 -1.782869 .000000
caspt2
O1 2.364214 1.225939 .000000
O2 -1.683805 2.759059 .000000
C3 -.020362 1.024359 .000000
C4 -1.100939 -1.649948 .000000
C5 .323471 -3.760138 .000000
H6 -.512522 -5.638946 .000000
H7 2.369876 -3.604588 .000000
H8 -3.156293 -1.781175 .000000
propenoic acid s1 casscf
O1 2.311927 1.194462 .000000
O2 -1.465557 2.900124 .000000
C3 -.290494 .890856 .000000
C4 -1.140602 -1.612121 .000000
C5 .401202 -3.798547 .000000
H6 -.434990 -5.651970 .000000
H7 2.431664 -3.703218 .000000
H8 -3.166404 -1.812244 .000000
caspt2
O1 2.325424 1.258056 .000000
O2 -1.496569 2.928573 .000000
C3 -.277192 .858023 .000000
C4 -1.121971 -1.651985 .000000
C5 .394492 -3.839928 .000000
H6 -.464362 -5.703661 .000000
H7 2.443994 -3.745606 .000000
pyrrole s0 casscf
C1 1.351055 1.852517 .000000
C2 2.112466 -.622925 .000000
N5 .000000 -2.113394 .000000
H6 .000000 -3.988474 .000000
H7 2.567605 3.470135 .000000
H8 3.964072 -1.434313 .000000
caspt2
C1 1.342117 1.859891 .000000
C2 2.127043 -.626872 .000000
N5 .000000 -2.118748 .000000
H6 .000000 -4.027979 .000000
H7 2.561706 3.497899 .000000
H8 3.996167 -1.445941 .000000
pyrrole 2a1 casscf
C1 1.383304 1.964847 .000000
C2 2.191596 -.709180 .000000
N5 .000000 -2.156778 .000000
H6 .000000 -4.030385 .000000
H7 2.598278 3.576377 .000000
H8 4.030367 -1.528685 .000000
caspt2
C1 1.394534 1.907469 .174130
C2 2.232526 -.677873 -.179038
N5 .000000 -2.117453 -.035741
H6 .000000 -4.007591 -.392629
H7 2.555765 3.569407 -.103088
H8 3.953194 -1.495888 .606141
pyrrole 2b2 casscf
C1 1.286720 1.961398 .000000
C2 2.135389 -.660468 .000000
N5 .000000 -2.234839 .000000
H6 .000000 -4.111090 .000000
H7 2.542498 3.544857 .000000
H8 3.989984 -1.453450 .000000
caspt2
C1 1.293594 1.963247 .000000
C2 2.156310 -.658992 .000000
N5 .000000 -2.245011 .000000
H6 .000000 -4.148247 .000000
H7 2.550247 3.573532 .000000
protonated schiff base (short) s0 casscf
C1 1.284219 -.001511 .000000
C2 -1.285278 .001285 .000000
C3 2.782697 2.253214 .000000
H4 2.278669 -1.773829 .000000
C5 -2.998333 2.151585 .000000
H6 -2.176454 -1.825834 .000000
N7 5.219820 2.228629 .000000
H8 1.919602 4.088308 .000000
C9 -5.523177 1.831427 .000000
H10 -2.245240 4.038911 .000000
H11 6.231900 3.829491 .000000
H12 6.203592 .606979 .000000
H13 -6.785061 3.418873 .000000
H14 -6.368414 -.015741 .000000
caspt2
C1 1.248997 -1.433924 .000000
C2 -1.349753 -1.415726 .000000
C3 2.720728 .789421 .000000
H4 2.226643 -3.237580 .000000
C5 -3.020808 .721186 .000000
H6 -2.266415 -3.254125 .000000
N7 5.197905 .774480 .000000
H8 1.850772 2.643890 .000000
C9 -5.556360 .371169 .000000
H10 -2.273492 2.630357 .000000
H11 6.213862 2.403026 .000000
H12 6.195515 -.869133 .000000
H13 -6.855319 1.950529 .000000
H14 -6.381750 -1.503569 .000000
protonated schiff base (short) s1 casscf 1
C1 1.406470 .119239 .000000
C2 -1.472893 .056575 .000000
C3 2.874160 2.260124 .000000
H4 2.307846 -1.699415 .000000
C5 -3.059633 2.092233 .000000
H6 -2.273211 -1.809835 .000000
N7 5.435844 2.207963 .000000
H8 2.075022 4.122157 .000000
C9 -5.725950 1.782534 .000000
H10 -2.338613 3.989921 .000000
H11 6.441730 3.800618 .000000
H12 6.402355 .588004 .000000
H14 -6.567681 -.063650 .000000
casscf 2
C1 -3.890813 -4.066135 .000000
C2 -1.838868 -2.416172 .000000
C3 -2.098163 .309203 .000000
C4 2.620348 1.099620 .000000
C5 -.000999 1.881139 .000000
N6 4.469847 2.842843 .000000
H7 -3.609574 -6.074113 .000000
H8 -5.798214 -3.372090 .000000
H9 .011655 -3.242190 .000000
H10 -3.958484 1.113516 .000000
H11 -.341859 3.884747 .000000
H12 3.216230 -.829329 .000000
H13 6.283140 2.339735 .000000
H14 4.108183 4.690954 .000000
caspt2
C1 1.266407 -1.377536 .000000
C2 -1.409771 -1.555419 .000000
C3 2.714670 .899777 .000000
H4 2.306680 -3.147827 .000000
C5 -3.013171 .606725 .000000
H6 -2.265184 -3.419326 .000000
N7 5.274596 .807426 .000000
H8 1.881028 2.768503 .000000
C9 -5.622953 .409267 .000000
H10 -2.184336 2.485247 .000000
H11 6.326401 2.409027 .000000
H12 6.229497 -.855620 .000000
H13 -6.818118 2.075108 .000000
H14 -6.550266 -1.422335 .000000
protonated schiff base (short) ci casscf
C1 1.433909 -.118011 .055869
C2 -1.321599 -.108660 .088300
C3 2.855249 1.434942 1.579347
H4 2.342670 -1.369952 -1.271607
C5 -2.782053 -1.703639 1.605470
H6 -2.305182 1.153054 -1.177973
N7 5.359216 1.521009 1.602104
H8 1.944057 2.698756 2.881564
C9 -5.380533 -1.625493 1.512301
H10 -1.849738 -3.000016 2.860617
H11 6.282111 2.688871 2.756130
H12 6.409666 .440506 .467484
H13 -6.512633 -2.837208 2.679560
caspt2
C1 1.270793 -.062212 -1.044750
C2 -1.477011 -.051200 -1.012264
C3 2.688727 1.497823 .486166
H4 2.194276 -1.327241 -2.384901
C5 -2.930551 -1.649769 .509656
H6 -2.475364 1.224154 -2.292403
N7 5.220037 1.579979 .505716
H8 1.765603 2.774344 1.800314
C9 -5.537597 -1.568995 .414334
H10 -1.986065 -2.957567 1.776333
H11 6.162708 2.766060 1.676831
H12 6.282875 .478573 -.650220
H13 -6.684218 -2.789494 1.591136
H14 -6.518833 -.280263 -.841669
protonated schiff base (long) s0 casscf
C1 -2.357395 1.363710 .000000
C2 -3.249476 -1.230699 .000000
C3 .000000 2.399703 .000000
C4 -5.755266 -1.767088 .000000
C5 2.500699 1.245771 .000000
C6 -6.787521 -4.320021 .000000
C7 4.506365 2.889368 .000000
C8 2.801307 -1.586986 .000000
C9 -9.281808 -4.819372 .000000
C10 7.092035 2.173624 .000000
N11 8.922388 3.799522 .000000
H12 -9.978301 -6.724972 .000000
H13 -3.857425 2.738528 .000000
H14 -1.936655 -2.772062 .000000
H15 .038986 4.431849 .000000
H16 -7.098330 -.235964 .000000
H17 -5.455493 -5.859458 .000000
H18 4.133511 4.888080 .000000
H19 -10.670976 -3.335049 .000000
H20 7.665613 .231028 .000000
H21 10.733420 3.254629 .000000
H22 8.600192 5.666155 .000000
H23 1.904082 -2.382525 1.657548
H25 4.746940 -2.202426 .000000
caspt2
C1 -2.364107 1.283434 .000000
C2 -3.184766 -1.280206 .000000
C3 .012515 2.368246 .000000
C5 2.446042 1.226953 .000000
C6 -6.727238 -4.351362 .000000
C7 4.503849 2.880351 .000000
C8 2.761890 -1.589492 .000000
C9 -9.242291 -4.811266 .000000
C10 7.024953 2.140929 .000000
N11 8.932093 3.758943 .000000
H12 -9.985122 -6.718481 .000000
H13 -3.902825 2.652673 .000000
H14 -1.856590 -2.835319 .000000
H15 .018367 4.423808 .000000
H16 -7.068739 -.276417 .000000
H17 -5.397657 -5.918739 .000000
H18 4.113486 4.899711 .000000
H19 -10.611280 -3.284542 .000000
H20 7.580636 .168232 .000000
H21 10.753926 3.163782 .000000
H22 8.641858 5.656878 .000000
H23 1.860880 -2.395235 1.674874
H25 4.727332 -2.194856 .000000
protonated schiff base (long) s1 casscf
C1 -2.502598 1.128799 .000000
C2 -3.202537 -1.350989 .000000
C3 .039295 2.313366 .000000
C4 -5.820307 -2.061577 .000000
C5 2.396025 1.266933 .000000
C6 -6.671518 -4.570046 .000000
C7 4.530968 3.052075 .000000
C8 2.872493 -1.552350 .000000
C9 -9.199959 -5.176314 .000000
C10 7.070015 2.464348 .000000
N11 8.905981 4.206535 .000000
H12 -9.820098 -7.106133 .000000
H13 -4.010811 2.494276 .000000
H14 -1.843660 -2.850961 .000000
H15 -.060434 4.342938 .000000
H16 -7.210091 -.576081 .000000
H17 -5.294459 -6.065775 .000000
H18 4.045525 5.027591 .000000
H19 -10.633164 -3.738574 .000000
H20 7.736396 .553000 .000000
H21 10.721362 3.710050 .000000
H22 8.528044 6.053281 .000000
H23 2.059661 -2.432102 1.662330
H25 4.859580 -2.015361 .000000
caspt2
C2 -3.174614 -1.383329 .000000
C3 -.028734 2.334577 .000000
C4 -5.750565 -2.120719 .000000
C5 2.365350 1.287284 .000000
C6 -6.545766 -4.659855 .000000
C7 4.453161 3.087058 .000000
C8 2.851540 -1.511655 .000000
C9 -9.050826 -5.315668 .000000
C10 6.999885 2.522948 .000000
N11 8.821914 4.315177 .000000
H12 -9.641979 -7.277376 .000000
H13 -4.065459 2.495175 .000000
H14 -1.772963 -2.876996 .000000
H15 -.121604 4.388455 .000000
H16 -7.189310 -.646805 .000000
H17 -5.115294 -6.134918 .000000
H18 3.919083 5.077731 .000000
H19 -10.529608 -3.895885 .000000
H20 7.706143 .597145 .000000
H21 10.684187 3.854671 .000000
H22 8.388846 6.185754 .000000
H23 2.031615 -2.392890 1.680638
H25 4.860050 -1.969254 .000000
Optimised
CASPT2 Energies (hartrees)
acetone s0 -192.5382095430 acetone s1 -192.3939095117
acrolein s0 -191.3300411209 acrolein s1 -191.2131958821 acrolein s1 ccpvdz -191.2483211134 acrolein s1 ccpvtz -191.4850089297
acrolein ci -191.1795699075, -191.1788403926
cis-butadiene -155.4283999875 cis-butadiene 2a1 -155.2394842200 cis-butadiene 1b2 -155.2227725459 cis-butadiene 1b2 ccpvdz -155.2867705066 cis-butadiene 1b2 ccpvtz -155.5069834120
cis-butadiene ci -155.2894989187, -155.2887148015 cis-butadiene c2 ci -155.2480650870, -155.2470193817 cis-butadiene c2v ci -155.2463972611, -155.2445733056
trans-butadiene -155.4488511107 trans-butadiene 2ag -155.2514646768 trans-butadiene 1bu -155.2215801921
trans-butadiene ci -155.2828341123, -155.2839130800
diazomethane s0 ccpvdz -148.3269574694 diazomethane s0 ccpvtz -148.5041959741 diazomethane s0 ccpvqz -148.5936790975 diazomethane s1 -148.2139414194 diazomethane s1 ccpvdz -148.2303979814 diazomethane s1 ccpvtz -148.4065810577 diazomethane s1 ccpvqz -148.4967300006
diazomethane ci -148.2426991497, -148.2464855115
propenoic acid anion s0 -265.8704213151 propenoic acid anion s1 -265.7428466246
pyrrole s0 -209.5042014419 pyrrole 2a1 -209.2980171178 pyrrole 2b2 -209.2752440456
ptd schiff base shrt s0 -249.0035530664 ptd schiff base shrt s1 -248.8667114837
ptd schiff base shrt ci -248.9188715810, -248.9196926769
