PAIR ORBITALS
PAIR 1 HAS ORBS 1  2
----------------------------
ROHF-GVB COUPLING PARAMETERS
----------------------------
F VECTOR (OCCUPANCIES)
1    0.9529411765
2    0.0470588235
Beide Orbitale sind aber sehr ungleichmäßig besetzt.
ALPHA COUPLING COEFFICEINTS
      1         2
1 0.9529412
2 0.0000000 0.0470588

BETA COUPLING COEFFICIENTS
      1          2
1 0.0000000
2 -0.2117647 0.0000000
NATURAL ORBITAL COEFFICIENTS
N.O.      PAIR CICOEF-S
1    0.9761870602   -0.2169304578
------------------------
ROHF-GVB SCF CALCULATION
------------------------
GVB STEP WILL USE 50204 WORDS OF MEMORY.
MAXIT= 30 NPUNCH= 2 SQCDF TOL=1.0000E-05
NUCLEAR ENERGY= 0.7207731745
EXTRAP=T DAMP=F SHIFT=F RSTRCT=F DIIS=F SOSCF=F
ITER EX TOTAL ENERGY E CHANGE SQCDF DIIS ERROR
0 0 -1.141922501 -1.141922501 0.040118149 0.000000000
1 1 -1.145988783 -0.004066282 0.008153342 0.000000000
2 2 -1.146108642 -0.000119860 0.004873220 0.000000000
3 3 -1.146114724 -0.000006082 0.002499592 0.000000000
4 0 -1.146115670 -0.000000946 0.000005395 0.000000000
5 1 -1.146115670 0.000000000 0.000002713 0.000000000
6 2 -1.146115670 0.000000000 0.000001268 0.000000000
-----------------
DENSITY CONVERGED
-----------------
FINAL ENERGY IS -1.1461156700 AFTER 6 ITERATIONS

FINAL ENERGY with NCO=1 NPAIR=0 IS -1.1268148531
6-31G-RHF:   IS -1.1268148531
experimental: -1.174 E_h
------------
EIGENVECTORS
------------
            1        2         3       4
         -0.6000  -0.0002   0.7742   0.9942
           A1G      A2U       A1G      A2U
1 H 1 S 0.333609  0.772164  0.761241 -0.830511
2 H 1 S 0.265187  0.575313 -0.687898  2.119979
3 H 2 S 0.333609 -0.772164  0.761241  0.830511
4 H 2 S 0.265187 -0.575313 -0.687898 -2.119979

Eigenvektoren mit 6-31G-RHF:
            1         2        3        4
         -0.5976   0.2400    0.7719   1.4122
           A1G       A2U      A1G       A2U
1 H 1 S 0.327882  0.121503  0.763726 -1.127486
2 H 1 S 0.270347  1.729745 -0.685887  1.353986
3 H 2 S 0.327882 -0.121503  0.763726  1.127486
4 H 2 S 0.270347 -1.729745 -0.685887 -1.353986

Das HOMO ist bei beiden Rechnungen sehr ähnlich. Die höheren Orbitale unterscheiden sich aber beträchtlich. Die GVB-Orbitale sind halt keine Ein-Elektronen-Wellenfunktionen mehr. Sie reflektieren die Elektronenkorrelation und ähneln daher einer CI-Rechnung.

-----------
GI ORBITALS
-----------
PAIR 1
1 2
1 H 1 S 0.559198 -0.074274
2 H 1 S 0.432425 -0.071124
3 H 2 S 0.074274 -0.559198
4 H 2 S 0.071124 -0.432425
... END OF ROHF-GVB SCF CALCULATION ...
6-31G-RHF:
1 2 3 4
-0.5976 0.2400 0.7719 1.4122
A1G A2U A1G A2U
1 H 1 S 0.327882 0.121503 0.763726 -1.127486
2 H 1 S 0.270347 1.729745 -0.685887 1.353986
3 H 2 S 0.327882 -0.121503 0.763726 1.127486
4 H 2 S 0.270347 -1.729745 -0.685887 -1.353986

... END OF ROHF-GVB SCF CALCULATION...
------------------------------
properties for the GVB density
------------------------------
-----------------
ENERGY COMPONENTS
-----------------
WAVEFUNCTION NORMALIZATION = 1.0000000000
ONE ELECTRON ENERGY = -2.4864681969
TWO ELECTRON ENERGY = 0.6195793525
NUCLEAR REPULSION ENERGY = 0.7207731745
------------------
TOTAL ENERGY = -1.1461156700
ELECTRON-ELECTRON POTENTIAL ENERGY = 0.6195793525
NUCLEUS-ELECTRON POTENTIAL ENERGY = -3.6607469129
NUCLEUS-NUCLEUS POTENTIAL ENERGY = 0.7207731745
------------------
TOTAL POTENTIAL ENERGY = -2.3203943859
TOTAL KINETIC ENERGY = 1.1742787159
VIRIAL RATIO (V/T) = 1.9760167279
---------------------------------------
MULLIKEN AND LOWDIN POPULATION ANALYSES
---------------------------------------
MULLIKEN ATOMIC POPULATION IN EACH MOLECULAR ORBITAL
1 2
1.976354 0.023646
1 0.988177 0.011823
2 0.988177 0.011823
----- POPULATIONS IN EACH AO -----
MULLIKEN LOWDIN
1 H 1 S 0.53487 0.50128
2 H 1 S 0.46513 0.49872
3 H 2 S 0.53487 0.50128
4 H 2 S 0.46513 0.49872
----- MULLIKEN ATOMIC OVERLAP POPULATIONS -----
(OFF-DIAGONAL ELEMENTS NEED TO BE MULTIPLIED BY 2)
1 2
1 0.6248987
2 0.3751013 0.6248987
TOTAL MULLIKEN AND LOWDIN ATOMIC POPULATIONS
ATOM MULL.POP. CHARGE LOW.POP. CHARGE
1 H 1.000000 0.000000 1.000000 0.000000
2 H 1.000000 0.000000 1.000000 0.000000

RHF:
WAVEFUNCTION NORMALIZATION = 1.0000000000
ONE ELECTRON ENERGY = -2.4999950970
TWO ELECTRON ENERGY = 0.6524070694
NUCLEAR REPULSION ENERGY = 0.7207731745
------------------
TOTAL ENERGY = -1.1268148531
ELECTRON-ELECTRON POTENTIAL ENERGY = 0.6524070694
NUCLEUS-ELECTRON POTENTIAL ENERGY = -3.6310514157
NUCLEUS-NUCLEUS POTENTIAL ENERGY = 0.7207731745
------------------
TOTAL POTENTIAL ENERGY = -2.2578711719
TOTAL KINETIC ENERGY = 1.1310563187
VIRIAL RATIO (V/T) = 1.9962499961
---------------------------------------
MULLIKEN AND LOWDIN POPULATION ANALYSES
---------------------------------------
MULLIKEN ATOMIC POPULATION IN EACH MOLECULAR ORBITAL
1
2.000000
1 1.000000
2 1.000000
----- POPULATIONS IN EACH AO -----
MULLIKEN LOWDIN
1 H 1 S 0.52135 0.49009
2 H 1 S 0.47865 0.50991
3 H 2 S 0.52135 0.49009
4 H 2 S 0.47865 0.50991
----- MULLIKEN ATOMIC OVERLAP POPULATIONS -----
(OFF-DIAGONAL ELEMENTS NEED TO BE MULTIPLIED BY 2)
1 2
1 0.5945962
2 0.4054038 0.5945962
TOTAL MULLIKEN AND LOWDIN ATOMIC POPULATIONS
ATOM MULL.POP. CHARGE LOW.POP. CHARGE
1 H 1.000000 0.000000 1.000000 0.000000
2 H 1.000000 0.000000 1.000000 0.000000