SPARTAN and CI
Dear CCLs,
I've got a problem understanding SPARTANS CI--output. Imagine you are
performing a MNDO calculation on water. Orbitals 1 to 4 are doubly
occupied. Now you want to do singles and doubles configuration
interaction with orbitals 3 to 6 active.
For the ground state, Spartan gives the following CI-wavefunction
(the complete output is given below):
0 -0.998742 => that's the ground state (HF) determinant
1 0.003359 => a singly excited determinant
3 0.003359 => a singly excited determinant
9 0.017222 => a doubly excited determinant
12 0.032083 => a doubly excited determinant
23 0.031287 => a doubly excited determinant
26 0.013703 => a doubly excited determinant
Thus the _singly_ excited determinants 1 and 3 enter the groundstate
wavefunction with 0.003359. How's that possible?
Thank's for your help
Michael
___________________________________________________________________
Dr. Michael E. Beck | privat:
Organisch--Chemisches Institut | Zschokkestr. 12a
Theoretische Gruppe, Prof. W. Thiel | CH--8037 Zuerich
Universitaet Zuerich | +41-1-271-54-39
Winterthurerstr. 190 |___________________________
CH--8057 Zuerich
Tel.: +41-1-635-6117 web : www.unizh.ch/oci/group.pages/
thiel/persons/beck/
Fax.: 6836 mail: mbeck' at \`oci.unizh.ch
___________________________________________________________________
Here's the complete SPARTAN output
SPARTAN SEMIEMPIRICAL PROGRAM: SGI/R10K Release 5.0.3
(Job run on ocisgi30)
Calculation started: Fri Aug 14 12:23:03 1998
Run type: Single point energy
Model: RHF/MNDO
Number of shells: 4
3 S shells
1 P shells
Number of basis functions: 6
Number of electrons: 8
Use of molecular symmetry enabled
Molecular charge: 0
Spin multiplicity: 1
Cartesian Coordinates (Angstroms)
Atom Label X Y Z
-- -------- ------------- ------------- -------------
H H1 0.0000000 -0.7570569 0.1874133
O O1 0.0000000 0.0000000 -0.3748267
H H2 0.0000000 0.7570569 0.1874133
Point Group = CNV Order = 2 Nsymop = 4
This system has 2 degrees of freedom
Interatomic distances (Angstroms)
1 2 3
1 0.000000 0.943000 1.514114
2 0.943000 0.000000 0.943000
3 1.514114 0.943000 0.000000
Angle 3 2 1 is 106.800 degrees
Angle 3 1 2 is 36.600 degrees
Angle 2 3 1 is 36.600 degrees
Highest occupied MO = #4
Huckel Guess...
Guess energy = -474.011396062
cycle # 1 Energy = -499.548338849
cycle # 2 Energy = -500.382719238
cycle # 3 Energy = -500.467977346
cycle # 4 Energy = -500.482152185
cycle # 5 Energy = -500.484942669 pseudo
cycle # 6 Energy = -500.485511347 pseudo
cycle # 7 Energy = -500.485628130 pseudo
cycle # 8 Energy = -500.485652173 pseudo
cycle # 9 Energy = -500.485657128 pseudo
Final Energy = -500.485658153 (rechecking after pseudodiagonalization)
Converged in 9 cycles
Convergence critera met in 9 cycles ...
Electronic energy = -500.485658 eV
Core repulsion energy = 149.060825 eV
Total Energy = -351.424834 eV
Performing integral transformation ...
Constructing singles ...
Constructing doubles ...
CI calculation performed using orbitals 3 to 6
Slater Determinants
State type configuration
-----------------------------------------------------------------
0 Ground state 11 00
11 00
1 Single 01 10
11 00
2 Single 01 01
11 00
3 Single 11 00
01 10
4 Single 11 00
01 01
5 Single 10 10
11 00
6 Single 10 01
11 00
7 Single 11 00
10 10
8 Single 11 00
10 01
9 Double 01 10
01 10
10 Double 01 10
01 01
11 Double 01 01
01 10
12 Double 01 01
01 01
13 Double 00 11
11 00
14 Double 01 10
10 10
15 Double 01 10
10 01
16 Double 01 01
10 10
17 Double 01 01
10 01
18 Double 10 10
01 10
19 Double 10 10
01 01
20 Double 10 01
01 10
21 Double 10 01
01 01
22 Double 11 00
00 11
23 Double 10 10
10 10
24 Double 10 10
10 01
25 Double 10 01
10 10
26 Double 10 01
10 01
Heats of Formation: HF -60.938 kcal/mol
CI -62.320 kcal/mol
Eigenvalues and eigenvectors of the CI matrix ...
0 1 2 3 4 5
eig: -0.059920 6.310075 7.511671 7.528376 8.243903 9.449156
OS: 0.123017 0.146661 0.000000 0.000000 0.758494
nm: 196.511126 165.076454 164.710152 150.414189 131.228648
spin: no yes no yes no
---------------------------------------------------------------------------
0 -0.998742 0.000000 0.000000 0.000000 0.000000 0.000000
1 0.003359 0.000000 0.000000 0.000000 0.000000 -0.707107
2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
3 0.003359 0.000000 0.000000 0.000000 0.000000 0.707107
4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
5 0.000000 0.705760 0.706022 0.000000 0.000000 0.000000
6 0.000000 0.000000 0.000000 0.704836 -0.705693 0.000000
7 0.000000 -0.705760 0.706022 0.000000 0.000000 0.000000
8 0.000000 0.000000 0.000000 -0.704836 -0.705693 0.000000
9 0.017222 0.000000 0.000000 0.000000 0.000000 0.000000
10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
12 0.032083 0.000000 0.000000 0.000000 0.000000 0.000000
13 0.000000 0.000000 0.000000 -0.010847 0.009463 0.000000
14 0.000000 -0.019114 0.009315 0.000000 0.000000 0.000000
15 0.000000 0.000000 0.000000 -0.029136 -0.025788 0.000000
16 0.000000 0.000000 0.000000 0.047322 0.035251 0.000000
17 0.000000 -0.039215 0.038023 0.000000 0.000000 0.000000
18 0.000000 -0.019114 -0.009315 0.000000 0.000000 0.000000
19 0.000000 0.000000 0.000000 -0.047322 0.035251 0.000000
20 0.000000 0.000000 0.000000 0.029136 -0.025788 0.000000
21 0.000000 -0.039215 -0.038023 0.000000 0.000000 0.000000
22 0.000000 0.000000 0.000000 0.010847 0.009463 0.000000
23 0.031287 0.000000 0.000000 0.000000 0.000000 0.000000
24 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
25 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
26 0.013703 0.000000 0.000000 0.000000 0.000000 0.000000
6 7 8 9 10 11
eig: 10.257741 10.323881 11.782136 15.801429 16.092334 16.430589
OS: 2.631401 0.813497 2.937839 0.000000 0.000000 0.000000
nm: 120.884315 120.109872 105.244074 78.473915 77.055325 75.468995
spin: no yes yes no no yes
---------------------------------------------------------------------------
0 0.000000 -0.007135 0.000000 0.000000 0.000000 0.018663
1 0.000000 -0.703839 0.000000 0.000000 0.000000 0.014371
2 -0.706960 0.000000 -0.701960 0.000000 0.012296 0.000000
3 0.000000 -0.703839 0.000000 0.000000 0.000000 0.014371
4 0.706960 0.000000 -0.701960 0.000000 -0.012296 0.000000
5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
9 0.000000 -0.066444 0.000000 0.000000 0.000000 -0.112892
10 0.009163 0.000000 -0.083163 0.000000 0.100365 0.000000
11 0.009163 0.000000 0.083163 0.000000 0.100365 0.000000
12 0.000000 -0.064357 0.000000 0.000000 0.000000 0.082687
13 0.000000 0.000000 0.000000 -0.408248 0.000000 0.000000
14 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
15 0.000000 0.000000 0.000000 0.408248 0.000000 0.000000
16 0.000000 0.000000 0.000000 0.408248 0.000000 0.000000
17 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
18 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
19 0.000000 0.000000 0.000000 0.408248 0.000000 0.000000
20 0.000000 0.000000 0.000000 0.408248 0.000000 0.000000
21 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
22 0.000000 0.000000 0.000000 -0.408248 0.000000 0.000000
23 0.000000 0.024536 0.000000 0.000000 0.000000 0.815618
24 -0.011107 0.000000 0.018348 0.000000 -0.699840 0.000000
25 -0.011107 0.000000 -0.018348 0.000000 -0.699840 0.000000
26 0.000000 0.003261 0.000000 0.000000 0.000000 -0.560736
12 13 14 15 16 17
eig: 17.333535 18.020974 19.015929 19.183426 19.365041 19.379897
OS: 0.000000 0.000000 0.000000 0.000000 0.000015 0.000000
nm: 71.537628 68.808711 65.208489 64.639131 64.032912 63.983829
spin: no no no yes yes yes
---------------------------------------------------------------------------
0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
1 0..000000 0.000000 0.000000 0.000000 0.000000 0.000000
2 0.000000 0.000000 0.000000 0.000000 0.029411 0.000000
3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
4 0.000000 0.000000 0.000000 0.000000 0.029411 0.000000
5 0.007689 0.000000 0.000000 0.000000 0.000000 -0.014835
6 0.000000 0.006805 0.001475 -0.004125 0.000000 0.000000
7 -0.007689 0.000000 0.000000 0.000000 0.000000 -0.014835
8 0.000000 -0.006805 -0.001475 -0.004125 0.000000 0.000000
9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
10 0.000000 0.000000 0.000000 0.000000 -0.093752 0.000000
11 0.000000 0.000000 0.000000 0.000000 0.093752 0.000000
12 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
13 0.000000 0.674224 0.207141 -0.569009 0.000000 0.000000
14 -0.571169 0.000000 0.000000 0.000000 0.000000 -0.571916
15 0.000000 0.153504 -0.586804 -0.369139 0.000000 0.000000
16 0.000000 0.147691 -0.335784 -0.199871 0.000000 0.000000
17 0.416782 0.000000 0.000000 0.000000 0.000000 0.415562
18 -0.571169 0.000000 0.000000 0.000000 0.000000 0.571916
19 0.000000 -0.147691 0.335784 -0.199871 0.000000 0.000000
20 0.000000 -0.153504 0.586804 -0.369139 0.000000 0.000000
21 0.416782 0.000000 0.000000 0.000000 0.000000 -0.415562
22 0.000000 -0.674224 -0.207141 -0.569009 0.000000 0.000000
23 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
24 0.000000 0.000000 0.000000 0.000000 0.700247 0.000000
25 0.000000 0.000000 0.000000 0.000000 -0.700247 0.000000
26 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
18 19 20 21 22 23
eig: 19.943584 20.380517 20.803840 22.406845 22.832961 23.342782
OS: 0.000001 0.000000 0.000006 0.000000 0.000003 0.000000
nm: 62.175385 60.842420 59.604381 55.340231 54.307455 53.121346
spin: yes no no yes yes no
---------------------------------------------------------------------------
0 -0.023708 0.000000 0.000000 0.000000 0.000000 0.000000
1 -0.020550 0.000000 0.000000 0.000000 0.000000 0.000000
2 0.000000 0.000000 0.000000 0.000000 0.000000 0.007492
3 -0.020550 0.000000 0.000000 0.000000 0.000000 0.000000
4 0.000000 0.000000 0.000000 0.000000 0.000000 -0.007492
5 0.000000 0.000000 0.042943 0.000000 0.036228 0.000000
6 0.000000 0.056191 0.000000 -0.044499 0.000000 0.000000
7 0.000000 0.000000 -0.042943 0.000000 0.036228 0.000000
8 0.000000 -0.056191 0.000000 -0.044499 0.000000 0.000000
9 0.071421 0.000000 0.000000 0.000000 0.000000 0.000000
10 0.000000 0.000000 0.000000 0.000000 0.000000 0.699888
11 0.000000 0.000000 0.000000 0.000000 0.000000 0.699888
12 0.123133 0.000000 0.000000 0.000000 0.000000 0.000000
13 0.000000 0.048965 0.000000 -0.097326 0.000000 0.000000
14 0.000000 0.000000 0.416415 0.000000 -0.415722 0.000000
15 0.000000 0.362282 0.000000 0.443176 0.000000 0.000000
16 0.000000 -0.602658 0.000000 -0.540502 0.000000 0.000000
17 0.000000 0.000000 0.569873 0.000000 -0.570844 0.000000
18 0.000000 0.000000 0.416415 0.000000 0.415722 0.000000
19 0.000000 0.602658 0.000000 -0.540502 0.000000 0.000000
20 0.000000 -0.362282 0.000000 0.443176 0.000000 0.000000
21 0.000000 0.000000 0.569873 0.000000 0.570844 0.000000
22 0.000000 -0.048965 0.000000 -0.097326 0.000000 0.000000
23 -0.561260 0.000000 0.000000 0.000000 0.000000 0.000000
24 0.000000 0.000000 0.000000 0.000000 0.000000 0.100504
25 0.000000 0.000000 0.000000 0.000000 0.000000 0.100504
26 -0.814443 0.000000 0.000000 0.000000 0.000000 0.000000
24 25 26
eig: 23.750830 26.793754 27.275329
OS: 0.000000 0.001123 0.000135
nm: 52.208701 46.279442 45.462329
spin: yes yes yes
---------------------------------------------------------------------------
0 0.004494 0.000000 -0.039162
1 0.006874 0.000000 0.062632
2 0.000000 -0.079923 0.000000
3 0.006874 0.000000 0.062632
4 0.000000 -0.079923 0.000000
5 0.000000 0.000000 0.000000
6 0.000000 0.000000 0.000000
7 0.000000 0.000000 0.000000
8 0.000000 0.000000 0.000000
9 -0.775560 0.000000 -0.613148
10 0.000000 0.695913 0.000000
11 0.000000 -0.695913 0.000000
12 0.615096 0.000000 -0.771030
13 0.000000 0.000000 0.000000
14 0.000000 0.000000 0.000000
15 0.000000 0.000000 0.000000
16 0.000000 0.000000 0.000000
17 0.000000 0.000000 0.000000
18 0.000000 0.000000 0.000000
19 0.000000 0.000000 0.000000
20 0.000000 0.000000 0.000000
21 0.000000 0.000000 0.000000
22 0.000000 0.000000 0.000000
23 -0.103953 0.000000 -0.085839
24 0.000000 0.096529 0.000000
25 0.000000 -0.096529 0.000000
26 0.096143 0.000000 -0.113204
eigenvalue 0 = -500.545578
eigenvalue 1 = -494.175583
eigenvalue 2 = -492.973987
eigenvalue 3 = -492.957282
eigenvalue 4 = -492.241755
eigenvalue 5 = -491.036502
eigenvalue 6 = -490.227917
eigenvalue 7 = -490.161777
eigenvalue 8 = -488.703522
eigenvalue 9 = -484.684229
eigenvalue 10 = -484.393324
eigenvalue 11 = -484.055070
eigenvalue 12 = -483.152123
eigenvalue 13 = -482.464684
eigenvalue 14 = -481.469729
eigenvalue 15 = -481.302232
eigenvalue 16 = -481.120617
eigenvalue 17 = -481.105761
eigenvalue 18 = -480.542074
eigenvalue 19 = -480.105141
eigenvalue 20 = -479.681818
eigenvalue 21 = -478.078813
eigenvalue 22 = -477.652697
eigenvalue 23 = -477.142876
eigenvalue 24 = -476.734828
eigenvalue 25 = -473.691904
eigenvalue 26 = -473.210329
Spin-allowed singlet excitations
State Energy OS nm
-----------------------------------------
2 7.511671 0.146661 165.076454
7 10.323881 0.813497 120.109872
8 11.782136 2.937839 105.244074
Ground State Dipole Moment:
u(x) = 0.000000 u(y) = 0.000000 u(z) = 1.773507 u(tot) = 1.773507
Ground State Atomic Charges
Atom Population Charge
------------------------------
H 1 0.838358 0.161642
O 2 6.323284 -0.323284
H 3 0.838358 0.161642
Ground State Bond Order Matrix
1 2 3
---------------------------------------------------------------------------
1 0.000000 0.966988 0.003462
2 0.966988 0.000000 0.966988
3 0.003462 0.966988 0.000000
State 2 Dipole Moment:
u(x) = 0.000000 u(y) = 0.000000 u(z) = -0.321723 u(tot) = 0.321723
State 2 Atomic Charges
------------------------------
H 1 1.143015 -0.143015
O 2 5.713970 0.286030
H 3 1.143015 -0.143015
State 2 Bond Order Matrix
1 2 3
---------------------------------------------------------------------------
1 0.000000 0.610875 0.059521
2 0.610875 0.000000 0.610875
3 0.059521 0.610875 0.000000
Gross electron populations over atoms (HF wavefunction):
Atom Population Net charge
------------------------------
1 0.837 0.163
2 6.326 -0.326
3 0.837 0.163
Bond Order Matrix
1 2 3
---------------------------------------------------------------------------
1 0.000000 0.970036 0.003445
2 0.970036 0.000000 0.970036
3 0.003445 0.970036 0.000000
Dipole Moment:
u(x) = 0.000000 u(y) = 0.000000 u(z) = 1.783296 u(tot) = 1.783296
Heat of Formation: -62.320 kcal/mol
** Archive file written to unit 12 **
Total Cpu time: 0 mins. 0.04 secs.
Total Wall time: 0 mins. 0.18 secs.
Calculation started: Fri Aug 14 12:23:03 1998
SPARTAN PROPERTIES PACKAGE: SGI/R10K Release 5.0.3
Total Cpu time: 0 mins. 0.00 secs.