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Next: 24 Full-CI calculations Up: GAMESS-UK part12 Previous: 22 ECP, CASSCF and   Contents

23 Table-CI Calculations of the Electronic Spectra of Pyridine

This example demonstrates the use of the Table-CI module in the calculation of the low-lying states of Pyridine. Specifically, we are involved in determining the disposition of the first ten 1A1 and 1A2 states, using a common set of orbitals (the X1A1 SCF-MOs) in a DZ plus Rydberg basis set of 91 functions. Five job files are presented below:
  1. Start-up closed-shell SCF calculation for the X1A1 state. Note the SUPER directive for compatibility with the subsequent CI calculation. Note also the particular syntax for siting the DZ basis on H: the third and fourth data fields are to provide an unscaled hydrogen basis, since the default specification will scale the two components by 1.2 (the more contracted) and 1.15 (the more diffuse component)
  2. 1M/1R Table-CI calculation of the X1A1 state.
  3. 6M/1R Table-CI calculation of the X1A1 state.
  4. 21M/10R Table-CI calculation of the ten lowest 1A1 states.
  5. 19M/10R Table-CI calculation of the ten lowest 1A2 states.
1.  Closed-shell SCF Job
          #!/bin/csh -f
          cd /scr1/user
          setenv ed2 pyred2
          setenv ed3 pyred3
          /scr1/wab/GAMESS-UK/bin/gamess << EOF
          title
          pyridine dz+bond-centred functions
          super off nosym
          zmat angstrom
          n
          x 1 1.0
          x 1 1.0 2 90.
          x 1 1.0 2 90. 3 90.
          c 1 c4n 3 90. 2 180.
          x 5 1.0 1 90. 3 0.0
          x 5 1.0 1 90. 4 0.0
          h 5 ch4 6 90. 1 180.
          c 1 c2n 2 c2nz 3 180.
          c 1 c2n 2 c2nz 3 0.0
          c 9 c2c3 1 ccn 2 180.
          c 10 c2c3 1 ccn 2 180.
          h 9 c2h6 1 nch2 2 0.0
          h 10 c2h6 1 nch2 2 0.0
          h 11 c3h5 9 c2c3h 1 180.
          h 12 c3h5 10 c2c3h 1 180.
          bq 1 1.39 3 90. 2 180.
          variables
          c4n 2.7845546
          ch4 1.0823078
          c2n 1.3372389
          c2nz 120.641858
          c2c3 1.3944571
          ccn 122.662269
          c2h6 1.0814291
          c3h5 1.0809550
          nch2 116.400433
          c2c3h 120.158516
          end
          basis
          dz h 1.0 1.0
          dz n
          dz c
          s bq
          1.0 0.021
          s bq
          1.0 0.008
          s bq
          1.0 0.0025
          p bq
          1.0 0.017
          p bq
          1.0 0.009
          d bq
          1.0 0.015
          d bq
          1.0 0.008
          end
          enter
          EOF
2.  1M/1R Table-CI Job for the X1A1 State

An examination of the SCF output reveals the following symmetry adapted basis functions, given the C2v geometry and DZ plus Rydberg basis set:

          =============================
          IRREP  NO. OF SYMMETRY ADAPTED
                 BASIS FUNCTIONS
          =============================
            1          45
            2          12
            3          28
            4           6
          =============================
Thus the orbital reordering performed by the Table-CI module will yield the sequence numbers 1-45 for the a1 MOs, 46-57 for the b1 MOs, 58-85 for the b2 MOs and 86-91 for the a2 MOs. We are both freezing and discarding orbitals in the subsequent CI calculations. Confining this to both a1 and b2 MOs, the first six orbitals of a1 symmetry and first four orbitals of b2 symmetry are to be frozen, and the eight highest energy orbitals of a1 symmetry and six highest of b2 are to be discarded. Thus the final sequence numbers for the active orbitals in the CI are 1-31 for the a1 MOs, 32-43 for the b1 MOs, 44-61 for the b2 MOs and 62-68 for the a2 MOs. The CONF data line specifying the reference configuration is based on the associated sequence numbers of these active orbitals.

          #!/bin/csh -f
          cd /scr1/user
          setenv ed2 pyred2
          setenv ed3 pyred3
          setenv ftn031 pyrtran
          setenv table /scr1/wab/GAMESS-UK/libs/TABLE
          /scr1/wab/GAMESS-UK/bin/gamess << EOF
          restart
          title
          pyridine dz+bond-centred functions
          super off nosym
          bypass scf
          zmat angstrom
          n
          x 1 1.0
          x 1 1.0 2 90.
          x 1 1.0 2 90. 3 90.
          c 1 c4n 3 90. 2 180.
          x 5 1.0 1 90. 3 0.0
          x 5 1.0 1 90. 4 0.0
          h 5 ch4 6 90. 1 180.
          c 1 c2n 2 c2nz 3 180.
          c 1 c2n 2 c2nz 3 0.0
          c 9 c2c3 1 ccn 2 180.
          c 10 c2c3 1 ccn 2 180.
          h 9 c2h6 1 nch2 2 0.0
          h 10 c2h6 1 nch2 2 0.0
          h 11 c3h5 9 c2c3h 1 180.
          h 12 c3h5 10 c2c3h 1 180.
          bq 1 1.39 3 90. 2 180.
          variables
          c4n 2.7845546
          ch4 1.0823078
          c2n 1.3372389
          c2nz 120.641858
          c2c3 1.3944571
          ccn 122.662269
          c2h6 1.0814291
          c3h5 1.0809550
          nch2 116.400433
          c2c3h 120.158516
          end
          basis
          dz h 1.0 1.0
          dz n
          dz c
          s bq
          1.0 0.021
          s bq
          1.0 0.008
          s bq
          1.0 0.0025
          p bq
          1.0 0.017
          p bq
          1.0 0.009
          d bq
          1.0 0.015
          d bq
          1.0 0.008
          end
          runtype ci
          mrdci
          adapt
          tran freeze discard
          6 0 4 0
          1 to 6 1 to 4
          8 0 6 0
          38 to 45 23 to 28
          select
          cntrl 22
          spin singlet
          symmetry 1
          conf
          0 1 2 3 4 5 32 33 44 45 46 62
          roots 1 1
          thresh 30 10
          ci
          diag
          title
          pyridine 1m1r ground state   dz + 3s2p2d rydberg basis
          extrap 3
          natorb
          civec 1
          putq aos 2
          enter
          EOF
3.  6M/1R Table-CI Job for the X1A1 State
          #!/bin/csh -f
          cd /scr1/user
          setenv ed2 pyred2
          setenv ed3 pyred3
          setenv ftn031 pyrtran
          setenv table /scr1/wab/GAMESS-UK/libs/TABLE
          /scr1/wab/GAMESS-UK/bin/gamess << EOF
          restart
          title
          pyridine dz+bond-centred functions
          super off nosym
          bypass scf
          zmat angstrom
          n
          x 1 1.0
          x 1 1.0 2 90.
          x 1 1.0 2 90. 3 90.
          c 1 c4n 3 90. 2 180.
          x 5 1.0 1 90. 3 0.0
          x 5 1.0 1 90. 4 0.0
          h 5 ch4 6 90. 1 180.
          c 1 c2n 2 c2nz 3 180.
          c 1 c2n 2 c2nz 3 0.0
          c 9 c2c3 1 ccn 2 180.
          c 10 c2c3 1 ccn 2 180.
          h 9 c2h6 1 nch2 2 0.0
          h 10 c2h6 1 nch2 2 0.0
          h 11 c3h5 9 c2c3h 1 180.
          h 12 c3h5 10 c2c3h 1 180.
          bq 1 1.39 3 90. 2 180.
          variables
          c4n 2.7845546
          ch4 1.0823078
          c2n 1.3372389
          c2nz 120.641858
          c2c3 1.3944571
          ccn 122.662269
          c2h6 1.0814291
          c3h5 1.0809550
          nch2 116.400433
          c2c3h 120.158516
          end
          basis
          dz h 1.0 1.0
          dz n
          dz c
          s bq
          1.0 0.021
          s bq
          1.0 0.008
          s bq
          1.0 0.0025
          p bq
          1.0 0.017
          p bq
          1.0 0.009
          d bq
          1.0 0.015
          d bq
          1.0 0.008
          end
          runtype ci
          mrdci
          adapt bypass
          tran freeze discard bypass
          6 0 4 0
          1 to 6 1 to 4
          8 0 6 0
          38 to 45 23 to 28
          select
          cntrl 22
          spin singlet
          symmetry 1
          conf
          0 1 2 3 4 5 32 33 44 45 46 62
          0 1 2 3 4 5 32 38 44 45 46 62
          0 1 2 3 4 5 32 33 44 45 46 65
          4 32 33 38 39  1 2 3 4 5  44 45 46 62
          4 32 39 62 65  1 2 3 4 5  33 44 45 46 
          4 33 38 62 65  1 2 3 4 5  32 44 45 46 
          roots 1 1
          thresh 30 10
          ci
          diag
          title
          pyridine 6m1r ground state   dz + 3s2p2d rydberg basis
          extrap 3
          natorb
          civec 1
          putq aos 2
          enter
          EOF
4.  21M/10R Table-CI Job for the 1A1 States
          #!/bin/csh -f
          cd /scr1/user
          setenv ed2 pyred2
          setenv ed3 pyred3
          setenv ftn031 pyrtran
          setenv table /scr1/wab/GAMESS-UK/libs/TABLE
          /scr1/wab/GAMESS-UK/bin/gamess << EOF
          restart
          title
          pyridine   dz+rydberg basis
          super off nosym
          bypass scf
          zmat angstrom
          n
          x 1 1.0
          x 1 1.0 2 90.
          x 1 1.0 2 90. 3 90.
          c 1 c4n 3 90. 2 180.
          x 5 1.0 1 90. 3 0.0
          x 5 1.0 1 90. 4 0.0
          h 5 ch4 6 90. 1 180.
          c 1 c2n 2 c2nz 3 180.
          c 1 c2n 2 c2nz 3 0.0
          c 9 c2c3 1 ccn 2 180.
          c 10 c2c3 1 ccn 2 180.
          h 9 c2h6 1 nch2 2 0.0
          h 10 c2h6 1 nch2 2 0.0
          h 11 c3h5 9 c2c3h 1 180.
          h 12 c3h5 10 c2c3h 1 180.
          bq 1 1.39 3 90. 2 180.
          variables
          c4n 2.7845546
          ch4 1.0823078
          c2n 1.3372389
          c2nz 120.641858
          c2c3 1.3944571
          ccn 122.662269
          c2h6 1.0814291
          c3h5 1.0809550
          nch2 116.400433
          c2c3h 120.158516
          end
          basis
          dz h 1.0 1.0
          dz n
          dz c
          s bq
          1.0 0.021
          s bq
          1.0 0.008
          s bq
          1.0 0.0025
          p bq
          1.0 0.017
          p bq
          1.0 0.009
          d bq
          1.0 0.015
          d bq
          1.0 0.008
          end
          runtype ci
          mrdci
          adapt bypass
          tran freeze discard bypass
          6 0 4 0
          1 to 6 1 to 4
          8 0 6 0
          38 to 45 23 to 28
          select
          cntrl 22
          spin singlet
          symmetry 1
          conf
          2 62 65 1 2 3 4 5 32 33 44 45 46
          2 33 34 1 2 3 4 5 32 44 45 46 62
          2 5 8 1 2 3 4 32 33 44 45 46 62
          2 62 63 1 2 3 4 5 32 33 44 45 46
          2 33 38 1 2 3 4 5 32 44 45 46 62
          2 33 35 1 2 3 4 5 32 44 45 46 62
          2 5 7 1 2 3 4 32 33 44 45 46 62
          2 33 37 1 2 3 4 5 32 44 45 46 62
          2 5 9 1 2 3 4 32 33 44 45 46 62
          2 62 64 1 2 3 4 5 32 33 44 45 46
          2 33 36 1 2 3 4 5 32 44 45 46 62
          2 5 11 1 2 3 4 32 33 44 45 46 62
          2 33 39 1 2 3 4 5 32 44 45 46 62
          2 32 34 1 2 3 4 5 33 44 45 46 62
          2 32 38 1 2 3 4 5 33 44 45 46 62
          4 5 8 33 38 1 2 3 4 32 44 45 46 62
          4 33 38 62 65 1 2 3 4 5 32 44 45 46
          4 32 33 34 38 1 2 3 4 5 44 45 46 62
          4 33 34 62 65 1 2 3 4 5 32 44 45 46
          4 32 38 62 63 1 2 3 4 5 33 44 45 46
          4 5 7 33 38 1 2 3 4 32 44 45 46 62
          roots 10 1 2 3 4 5 6 7 8 9 10
          thresh 30 10
          ci
          diag
          title
          pyridine 21m10r 1a1    dz + 3s2p2d rydberg basis
          extrap 3
          enter
          EOF
5.  19M/10R Table-CI Job for the 1A2 States
          #!/bin/csh -f
          cd /scr1/user
          setenv ed2 pyred2
          setenv ed3 pyred3
          setenv ftn031 pyrtran
          setenv table /scr1/wab/GAMESS-UK/libs/TABLE
          /scr1/wab/GAMESS-UK/bin/gamess << EOF
          restart
          title
          pyridine  dz+rydberg basis
          super off nosym
          bypass scf
          zmat angstrom
          n
          x 1 1.0
          x 1 1.0 2 90.
          x 1 1.0 2 90. 3 90.
          c 1 c4n 3 90. 2 180.
          x 5 1.0 1 90. 3 0.0
          x 5 1.0 1 90. 4 0.0
          h 5 ch4 6 90. 1 180.
          c 1 c2n 2 c2nz 3 180.
          c 1 c2n 2 c2nz 3 0.0
          c 9 c2c3 1 ccn 2 180.
          c 10 c2c3 1 ccn 2 180.
          h 9 c2h6 1 nch2 2 0.0
          h 10 c2h6 1 nch2 2 0.0
          h 11 c3h5 9 c2c3h 1 180.
          h 12 c3h5 10 c2c3h 1 180.
          bq 1 1.39 3 90. 2 180.
          variables
          c4n 2.7845546
          ch4 1.0823078
          c2n 1.3372389
          c2nz 120.641858
          c2c3 1.3944571
          ccn 122.662269
          c2h6 1.0814291
          c3h5 1.0809550
          nch2 116.400433
          c2c3h 120.158516
          end
          basis
          dz h 1.0 1.0
          dz n
          dz c
          s bq
          1.0 0.021
          s bq
          1.0 0.008
          s bq
          1.0 0.0025
          p bq
          1.0 0.017
          p bq
          1.0 0.009
          d bq
          1.0 0.015
          d bq
          1.0 0.008
          end
          runtype ci
          mrdci
          adapt bypass
          tran freeze discard bypass
          6 0 4 0
          1 to 6 1 to 4
          8 0 6 0
          38 to 45 23 to 28
          select
          cntrl 22
          spin singlet
          symmetry 4
          conf
          2 5 65 1 2 3 4 32 33 44 45 46 62
          2 33 47 1 2 3 4 5 32 44 45 46 62
          2 5 63 1 2 3 4 32 33 44 45 46 62
          2 33 48 1 2 3 4 5 32 44 45 46 62
          2 8 62 1 2 3 4 5 32 33 44 45 46
          2 7 62 1 2 3 4 5 32 33 44 45 46
          2 33 50 1 2 3 4 5 32 44 45 46 62
          2 5 64 1 2 3 4 32 33 44 45 46 62
          2 33 49 1 2 3 4 5 32 44 45 46 62
          2 6 62 1 2 3 4 5 32 33 44 45 46
          4 5 33 38 65 1 2 3 4 32 44 45 46 62
          4 5 33 38 63 1 2 3 4 32 44 45 46 62
          4 33 47 62 65 1 2 3 4 5 32 44 45 46
          4 5 33 34 65 1 2 3 4 32 44 45 46 62
          4 7 33 38 62 1 2 3 4 5 32 44 45 46
          4 33 47 62 63 1 2 3 4 5 32 44 45 46
          4 8 33 38 62 1 2 3 4 5 32 44 45 46
          4 5 33 34 63 1 2 3 4 32 44 45 46 62
          4 33 48 62 63 1 2 3 4 5 32 44 45 46
          roots 10 1 2 3 4 5 6 7 8 9 10
          thresh 30 10
          ci
          diag
          title
          pyridine 19m10r 1a2  dz + 3s2p2d rydberg basis
          extrap 3
          enter
          EOF


next up previous contents
Next: 24 Full-CI calculations Up: GAMESS-UK part12 Previous: 22 ECP, CASSCF and   Contents