Output-File

H2, 6-311G-Basissatz, S0 und S1

Der folgende Teil gibt den gewählten Basissatz wieder und zeigt einige weitere Schlüselwörter an.

BASIS OPTIONS
-------------
GBASIS=N311   IGAUSS= 6   POLAR=NONE    NDFUNC= 0   DIFFSP= F
NPFUNC= 0     DIFFS= F

ATOMIC BASIS SET
----------------
THE CONTRACTED PRIMITIVE FUNCTIONS HAVE BEEN UNNORMALIZED
THE CONTRACTED BASIS FUNCTIONS ARE NOW NORMALIZED TO UNITY

SHELL TYPE PRIM  EXPONENT   CONTRACTION COEFFICIENTS

H
4       S   1    33.865000   0.255069 ( 0.025494)
4       S   2     5.094790   0.460109 ( 0.190373)
4       S   3     1.158790   0.678321 ( 0.852161)
5       S   4     0.325840   0.307371 ( 1.000000)
6       S   5     0.102741   0.129336 ( 1.000000)

TOTAL NUMBER OF SHELLS = 6
TOTAL NUMBER OF BASIS FUNCTIONS = 6

Diesen Basissatz kann man auffassen als bestehend aus einen 1s-AO (gebildet aus 3 Gauss-Funktionen (NGAUS=6 hätte man hier auch weglassen können), einem 2s-AO (gebildet aus einer Gauss-Funktion) und einem 3s-AO (gebildet aus einer Gauss-Funktion), also 311.

Symmetrie-Angaben

SYMMETRIES FOR INITIAL GUESS ORBITALS FOLLOW. BOTH SET(S).
1 ORBITALS ARE OCCUPIED ( 0 CORE ORBITALS).
1=A1G   2=A2U   3=A1G   4=A1G   5=A2U   6=A2U

RHF-Rechnung
FINAL ENERGY IS -1.1280332035 AFTER 7 ITERATIONS
(mit 6-31G      -1.1268148531 AFTER 7 ITERATIONS)
 (mit STO-6G war sie -1.1256665168 AFTER 2 ITERATIONS)

Es folgt die Darstellung der Eigenvektoren:
------------
EIGENVECTORS
------------
           1         2         3         4         5
        -0.5977    0.1697   0.3056    0.6540    2.4062
          A1G       A2U       A1G       A2U       A1G
1 H 1 S 0.192724  0.080247 -0.049761 -0.088485 -1.081254
2 H 1 S 0.295119 -0.040911 -0.709502 -1.750985  1.217299
3 H 1 S 0.126017  2.291587  0.846980  2.212177 -0.486589
4 H 2 S 0.192724 -0.080247 -0.049761  0.088485 -1.081254
5 H 2 S 0.295119  0.040911 -0.709502  1.750985  1.217299
6 H 2 S 0.126017 -2.291587  0.846980 -2.212177 -0.486589

             6
           2.7569
            A2U
1 H 1 S -1.132096
2 H 1 S  1.800100
3 H 1 S -1.201279
4 H 2 S  1.132096
5 H 2 S -1.800100
6 H 2 S  1.201279

Da als AO's jetzt die 1s-, 2s- und 3s-AO's (2s und 3s bedeutet nicht, dass das die "richtigen" H-Atom-Orbitale sind, s. hier) verwendet wurden, können 6 MO's gebildet werden.

...... END OF RHF CALCULATION ......


 mit diesen Wellenfunktionen wird die CI-Rechnung durchgeführt

Es folgt die Energieberechnung mit CI

-CORE- -INTERNAL- -EXTERNAL-
NFZC= 0  NDOC= 1  NEXT= 0   NMCC= 0  NAOS= 0  NFZV= 0    NBOS= 0
NALP= 0  NVAL= 5

THE MAXIMUM ELECTRON EXCITATION WILL BE 2

SYMMETRIES FOR THE 0 CORE, 6 ACTIVE, 0 EXTERNAL MO-S ARE
ACTIVE= A   A   A   A   A   A
              DOC VAL VAL VAL VAL VAL

STATE # 1 ENERGY = -1.153402058

CSF   COEF      OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
 1   0.992534    2 0 0 0 0 0
10  -0.063316    0 0 0 2 0 0
19   0.071161    0 1 0 1 0 0

mit 6-31G, NVAL=2: -1.145980081
           NVAL=3: -1.151601456

Man erkennt, dass der Grundzustand im Wesentlichen durch das doppelt besetzte bindende MO gebildet wird. Dazu kommen Beiträge von zwei doppelt angeregten Zuständen.

STATE # 2 ENERGY = -0.646940607

CSF   COEF     OCCUPANCY (IGNORING CORE)
---   ----     --------- --------- -----
16   0.984276   1 1 0 0 0 0
20  -0.168321   0 1 1 0 0 0

mit 6-31G, NVAL=3: -0.587199094

STATE # 3 ENERGY = -0.518530294

CSF   COEF       OCCUPANCY (IGNORING CORE)
---   ----       --------- --------- -----
10   0.057948     0 0 0 2 0 0
11   0.978600     1 0 1 0 0 0
15  -0.185573     0 0 2 0 0 0

Zum Vergleich: 6-31G, NVAL=3
STATE # 3 ENERGY = -0.105124648
CSF   COEF      OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
 3 -0.096118     0 0 0 2
 4  0.981348     1 0 1 0
 6  0.081646     0 0 2 0
 8  0.079879     0 1 0 1
10  0.121072     0 2 0 0
Man erkennt, deutlich höhere Energie und ganz andere CI.

STATE # 4 ENERGY = -0.193047632
CSF   COEF      OCCUPANCY (IGNORING CORE)
---   ----      --------- --------- -----
 7  0.978418     1 0 0 1 0 0
20 -0.190660     0 1 1 0 0 0

STATE # 5 ENERGY = -0.067908085
CSF   COEF     OCCUPANCY (IGNORING CORE)
--- ---- --------- --------- -----
 1  0.072253    2 0 0 0 0 0
15 -0.096346    0 0 2 0 0 0
17 -0.062364    0 1 0 0 0 1
19 -0.481113    0 1 0 1 0 0
21  0.865407    0 2 0 0 0 0

STATE # 6 ENERGY = 0.103667073
CSF   COEF     OCCUPANCY (IGNORING CORE)
---   ----     --------- --------- -----
2  -0.060726    1 0 0 0 0 1
7   0.190573    1 0 0 1 0 0
14 -0.506513    0 0 1 1 0 0
16  0.144435    1 1 0 0 0 0
20  0.823292    0 1 1 0 0 0

Dann Energie und natürliche MO's des Grundzustandes

--------------------------------------
CI DENSITY MATRIX AND NATURAL ORBITALS
--------------------------------------
NFLGDM= 1 1 0 0 0 0
NWORD= 0 IROOT= 2 IBLOCK= 0
THE ENERGY OF STATE -IROOT- IS -0.6469406072

NFLGDM bedeutet, die Eigenschaften der ersten beiden Elektronenzustände von insgesamt 6 Zuständen werden berechnet.

CI EIGENSTATE 1 TOTAL ENERGY = -1.1534020576

NATURAL ORBITALS IN ATOMIC ORBITAL BASIS
----------------------------------------
           1         2          3        4         5
         1.9703    0.0246    0.0047    0.0002   0.0001
1 H 1 S 0.197420  0.375356 -0.558148 -0.966906 -0.926405
2 H 1 S 0.291376  0.876988 -0.042734  1.358875  1.409106
3 H 1 S 0.126370  0.034396  0.513333  0.265724 -0.830991
4 H 2 S 0.197420 -0.375356 -0.558148  0.966906 -0.926405
5 H 2 S 0.291376 -0.876988 -0.042734 -1.358875  1.409106
6 H 2 S 0.126370 -0.034396  0.513333 -0.265724 -0.830991

             6
          0.0000
1 H 1 S  0.469160
2 H 1 S -1.921544
3 H 1 S  3.393579
4 H 2 S -0.469160
5 H 2 S  1.921544
6 H 2 S -3.393579

CI EIGENSTATE 2 TOTAL ENERGY = -0.6469406072

NATURAL ORBITALS IN ATOMIC ORBITAL BASIS
----------------------------------------
                 1         2        3         4         5
              0.9998    0.9998    0.0002    0.0002   0.0000
 1  H  1 S   0.058965  0.250068  0.983188 -1.011485  0.570768
 2  H  1 S  -0.004395  0.351618 -0.487975  0.938666 -2.463705
 3  H  1 S   2.265327  0.004740 -0.233547 -0.164499  2.530202
 4  H  2 S  -0.058965  0.250068 -0.983188 -1.011485 -0.570768
 5  H  2 S   0.004395  0.351618  0.487975  0.938666  2.463705
 6  H  2 S  -2.265327  0.004740  0.233547 -0.164499 -2.530202

                 6
              0.0000
 1  H  1 S   0.350848
 2  H  1 S  -1.033236
 3  H  1 S   0.971052
 4  H  2 S   0.350848
 5  H  2 S  -1.033236
 6  H  2 S   0.971052

PROPERTIES WILL BE COMPUTED FOR ROOT 2
-----------------------------
properties for the CI density
-----------------------------
-----------------
ENERGY COMPONENTS
-----------------
WAVEFUNCTION NORMALIZATION = 1.0000000000
ONE ELECTRON ENERGY = -1.7527831598
TWO ELECTRON ENERGY = 0.3850693782
NUCLEAR REPULSION ENERGY = 0.7207731745
------------------
TOTAL ENERGY = -0.6469406072
ELECTRON-ELECTRON POTENTIAL ENERGY = 0.3850693782
NUCLEUS-ELECTRON POTENTIAL ENERGY = -2.7891539882
NUCLEUS-NUCLEUS POTENTIAL ENERGY = 0.7207731745
------------------
TOTAL POTENTIAL ENERGY = -1.6833114355
TOTAL KINETIC ENERGY = 1.0363708283
VIRIAL RATIO (V/T) = 1.6242366048
---------------------------------------
MULLIKEN AND LOWDIN POPULATION ANALYSES
---------------------------------------
MULLIKEN ATOMIC POPULATION IN EACH MOLECULAR ORBITAL
      1       2        3        4        5
  0.999780 0.999780 0.000204 0.000204 0.000016
1 0.499890 0.499890 0.000102 0.000102 0.000008
2 0.499890 0.499890 0.000102 0.000102 0.000008

     6
  0.000016
1 0.000008
2 0.000008

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.
----- POPULATIONS IN EACH AO -----
        MULLIKEN  LOWDIN
1 H 1 S  0.19134  0.19510
2 H 1 S  0.31509  0.36385
3 H 1 S  0.49358  0.44105
4 H 2 S  0.19134  0.19510
5 H 2 S  0.31509  0.36385
6 H 2 S  0.49358  0.44105

----- MULLIKEN ATOMIC OVERLAP POPULATIONS -----
(OFF-DIAGONAL ELEMENTS NEED TO BE MULTIPLIED BY 2)
      1          2
1  5.5319177
2 -4.5319177  5.5319177

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