!
! H4 2plus, CI
!
$CONTRL SCFTYP=RHF MULT=1 ICHARG=2 RUNTYP=ENERGY COORD=UNIQUE
CITYP=GUGA
$END
$SYSTEM TIMLIM=1000 MEMORY=5000000 $END
$BASIS GBASIS=STO NGAUSS=6 $END
$CIDRT
GROUP=D2H IEXCIT=2
NFZC=0
NDOC=1
NALP=0
NVAL=3
$END
$GUGDIA
NSTATE=4
$END
$GUGDM
IROOT=1
NFLGDM(1)=1 $END
$GUGDM2 WSTATE(1)=1.0,0.0 $END
$GUESS GUESS=HUCKEL $END
$DATA
H4 2plus, CI
DNH 2
H 1.0 0.000 0.500 0.000
H 1.0 0.000 1.500 0.000
$END
THE 6 LOWEST DIAGONAL ELEMENTS OF THE HAMILTONIAN ARE
-0.9028218 (CSF 1) -0.3532036 (CSF 4) -0.2818739 (CSF 5)
0.3120039 (CSF 6) 0.3863962 (CSF 3) 1.0418349 (CSF 2)
SOLUTION FOUND WITH DIRECT METHOD
STATE # 1 ENERGY = -0.954596443
CSF COEF OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
1 0.963278 2000
3 -0.104224 0101
4 -0.237105 0200
STATE # 2 ENERGY = -0.456908767
CSF COEF OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
1 0.205823 2000
2 -0.089316 0002
4 0.769000 0200
5 -0.596019 1010
STATE # 3 ENERGY = -0.295612639
CSF COEF OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
1 0.119297 2000
3 0.253104 0101
4 0.527400 0200
5 0.750907 1010
6 -0.280305 0020
STATE # 4 ENERGY = 0.183488254
CSF COEF OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
1 0.107080 2000
2 -0.098314 0002
3 0.620868 0101
6 0.768431 0020
RENORMALIZED DAVIDSON CORRECTION FOR 1-REFERENCE CI.
C0SQ= 0.927905 EREF= -0.902822 E-E(REF)= 0.051775 E(Q)= 0.004023
GIVES A E(SD+Q) ESTIMATE OF -0.9586191404
...... END OF CI-MATRIX DIAGONALIZATION ......
--------------------------------------
CI DENSITY MATRIX AND NATURAL ORBITALS
--------------------------------------
NFLGDM= 1 0 0 0
NWORD= 0 IROOT= 1 IBLOCK= 0
THE ENERGY OF STATE -IROOT- IS -0.9545964433
NUMBER OF STATES = 4
NUMBER OF CONFIGURATIONS = 6
NUMBER OF 1E-LOOPS = 12
CI EIGENSTATE 1 TOTAL ENERGY = -0.9545964433
NATURAL ORBITALS IN ATOMIC ORBITAL BASIS
----------------------------------------
1 2 3 4
1.8577 0.1368 0.0051 0.0004
1 H 1 S -0.468039 0.698869 -0.474927 -0.952777
2 H 2 S -0.468039 -0.698869 -0.474927 0.952777
3 H 3 S -0.215781 0.307258 0.777678 0.789830
4 H 4 S -0.215781 -0.307258 0.777678 -0.789830
Die RHF-Eigenvektoren waren:
------------
EIGENVECTORS
------------
1 2
3 4
-1.3305
-0.8234 -0.4598 0.0595
AG B2U
AG B2U
1 H 1 S 0.478444 0.363881 -0.464444
1.124185
2 H 2 S 0.478444 -0.363881 -0.464444
-1.124185
3 H 3 S 0.198502 0.539997
0.782267 -0.653179
4 H 4 S 0.198502 -0.539997 0.782267
0.653179
...... END OF RHF CALCULATION ......
Eigentlich hatte ich angenommen, dass
die Eigenfunktionen dieselben bleiben, nur dass bei den natürlichen Orbitalen
oben, statt der Orbitalenergie die Elektronenbesetzung angegeben ist. Dem ist
aber offensichtlich nicht so.
PROPERTIES WILL BE COMPUTED FOR ROOT 1
...... END OF DENSITY MATRIX CALCULATION ......
-----------------------------
properties for the CI density
-----------------------------
-----------------
ENERGY COMPONENTS
-----------------
WAVEFUNCTION NORMALIZATION = 1.0000000000
ONE ELECTRON ENERGY = -3.6786678120
TWO ELECTRON ENERGY = 0.4309699554
NUCLEAR REPULSION ENERGY = 2.2931014134
------------------
TOTAL ENERGY = -0.9545964433
ELECTRON-ELECTRON POTENTIAL ENERGY = 0.4309699554
NUCLEUS-ELECTRON POTENTIAL ENERGY = -4.7311444044
NUCLEUS-NUCLEUS POTENTIAL ENERGY = 2.2931014134
------------------
TOTAL POTENTIAL ENERGY = -2.0070730357
TOTAL KINETIC ENERGY = 1.0524765924
VIRIAL RATIO (V/T) = 1.9070001653
ohne CI
-----------------
ENERGY COMPONENTS
-----------------
WAVEFUNCTION NORMALIZATION = 1.0000000000
ONE ELECTRON ENERGY = -3.7307542637
TWO ELECTRON ENERGY = 0.5348310029
NUCLEAR REPULSION ENERGY = 2.2931014134
------------------
TOTAL ENERGY = -0.9028218474
ELECTRON-ELECTRON POTENTIAL ENERGY = 0.5348310029
NUCLEUS-ELECTRON POTENTIAL ENERGY = -4.7330300452
NUCLEUS-NUCLEUS POTENTIAL ENERGY = 2.2931014134
------------------
TOTAL POTENTIAL ENERGY = -1.9050976290
TOTAL KINETIC ENERGY = 1.0022757815
VIRIAL RATIO (V/T) = 1.9007718874
---------------------------------------
MULLIKEN AND LOWDIN POPULATION ANALYSES
---------------------------------------
MULLIKEN ATOMIC POPULATION IN EACH MOLECULAR ORBITAL
1 2 3 4
1.857728 0.136778 0.005068 0.000425
1 0.724796 0.044688 0.000557 0.000074
2 0.724796 0.044688 0.000557 0.000074
3 0.204068 0.023701 0.001977 0.000139
4 0.204068 0.023701 0.001977 0.000139
WARNING! CI POPULATIONS SHOWN ABOVE ARE FOR THE NATURAL ORBITALS.
IGNORE THE ABOVE DATA FOR CI FUNCTIONS WHICH ARE NOT OF -FORS- TYPE.
THE FOLLOWING POPULATIONS ARE CORRECT FOR ANY CI WAVEFUNCTION.
ohne CI
MULLIKEN ATOMIC POPULATION IN EACH MOLECULAR ORBITAL
1
2.000000
1 0.802357
2 0.802357
3 0.197643
4 0.197643
1
2.000000
1 0.802357
2 0.802357
3 0.197643
4 0.197643
keine Unterschiede
----- POPULATIONS IN EACH AO -----
MULLIKEN LOWDIN
1 H 1 S 0.77011 0.75098
2 H 2 S 0.77011 0.75098
3 H 3 S 0.22989 0.24902
4 H 4 S 0.22989 0.24902
ohne CI
----- POPULATIONS IN EACH AO -----
MULLIKEN LOWDIN
1 H 1 S 0.80236 0.78338
2 H 2 S 0.80236 0.78338
3 H 3 S 0.19764 0.21662
4 H 4 S 0.19764 0.21662
Unterschiede
----- MULLIKEN ATOMIC OVERLAP POPULATIONS -----
(OFF-DIAGONAL ELEMENTS NEED TO BE MULTIPLIED BY 2)
1 2 3 4
1 0.4752887
2 0.1693402 0.4752887
3 0.1066977 0.0187884 0.1027420
4 0.0187884 0.1066977 0.0016569 0.1027420
ohne CI
----- MULLIKEN ATOMIC OVERLAP POPULATIONS -----
(OFF-DIAGONAL ELEMENTS NEED TO BE MULTIPLIED BY 2)
1 2 3 4
1 0.4578166
2 0.2274135 0.4578166
3 0.0943521 0.0227750 0.0788064
4 0.0227750 0.0943521 0.0017094 0.0788064
TOTAL MULLIKEN AND LOWDIN ATOMIC POPULATIONS
ATOM MULL.POP. CHARGE LOW.POP. CHARGE
1 H 0.770115 0.229885 0.750978 0.249022
2 H 0.770115 0.229885 0.750978 0.249022
3 H 0.229885 0.770115 0.249022 0.750978
4 H 0.229885 0.770115 0.249022 0.750978
ohne CI
TOTAL MULLIKEN AND LOWDIN ATOMIC POPULATIONS
ATOM MULL.POP. CHARGE LOW.POP. CHARGE
1 H 0.802357 0.197643 0.783380 0.216620
2 H 0.802357 0.197643 0.783380 0.216620
3 H 0.197643 0.802357 0.216620 0.783380
4 H 0.197643 0.802357 0.216620 0.783380