! EXAM45. ! triples-corrected excited state energies by coupled cluster EOM, ! from a closed shell ground state. ! Molecule is CH2, with 43 AOs and 41 MOs in aug-cc-pVDZ basis. ! ! a priori, we know that methylene has two valence excited singlet ! states, 1-B-1 and a second 1-A-1, with the latter being a double ! excitation from the lowest singlet 1-A-1. ! ! reference 1-A-1: FINAL ENERGY= -38.8841290160, in 11 iters ! reference 1-A-1: MBPT(2) E= -38.9999600236 ! reference 1-A-1: CCSD ENERGY= -39.0279559403, in 16 iters, T1=0.00998093 ! reference 1-A-1 lambda equation requires 7 iterations. ! EOM-CCSD level results are ! 1-A-1: EOM-CCSD= -38.80419384, 15 iters, R2=0.7535(4**2 -> 5**2) ! 1-B-1: EOM-CCSD= -38.96328855, 7 iters, R1=0.6169(4**2 -> 4**1,5**1) ! excited state lambda equations take 10, 7, 6 iterations. ! the bright state, 1-1A1 to 1B1 at 1.76 eV has EOM-CCSD transition info ! RIGHT TRANSITION MOM. 0.28097065 0.00000000 0.00000000 ! LEFT TRANSITION MOM. 0.30086244 0.00000000 0.00000000 ! DIPOLE STRENGTH 0.08453352 0.00000000 0.00000000 ! OSCILLATOR STRENGTH 0.00364437 0.00000000 0.00000000 ! triples corrected energies are ! g.s.: GROUND STATE CR-CC(2,3),D TOTAL E= -39.0318193002 ! 1-B-1: CR-EOMCC(2,3) OR CR-EOMCCSD(T)_L E= -38.9658047536 ! 1-A-1: CR-EOMCC(2,3) OR CR-EOMCCSD(T)_L E= -38.8539785232 ! with column D just below being the best overal results, ! SUMMARY OF CR-EOMCC(2,3) RESULTS FOR ALL STATES ! EXCITATION ENERGIES IN EV, 1 H = 27.211396 EV ! STATE EOMCCSD (2,3),D (2,3),A (2,3),B (2,3),C ! B1 1.760 1.796 1.789 1.788 1.796 ! A1 6.089 4.839 5.134 5.192 4.834 ! The EOM-CCSD level dipole moment for 2-1A1 is 0.353331 Debye. ! $contrl scftyp=rhf cctyp=cr-eoml runtyp=energy ispher=1 $end $system mwords=1 $end $basis gbasis=accd $end $guess guess=huckel $end $ccinp ccprp=.true. $end $eominp nstate(1)=1,0,1,0 iroot(1)=1,1 ccprpe=.true. minit=1 noact=3 nuact=5 moact(1)=2,3,4, 8,9,10,11,12 $end $data methyelene...aug-cc-pVDZ basis...excited states...1-1A1 state's MP2 geometry Cnv 2 CARBON 6.0 0.0 0.0 0.0054633173 HYDROGEN 1.0 0.0 -0.8669990485 -0.7027316586 $end