CI

1
?????? ?? ????????????????? ??????????????
(CI) ????? ????? ?????????? CI
2
???? ?? ?????? CI-????????????
??????, ?????? ?????????????? ?????? ?? ?????, ??
??????? ???

• ?????????? ?? ?????????? (UV/VIS) ???????

• ?????????? ?? ??????? ??????? ??? ????????
  ?????????

• ???????? ?? ????????-?????????? ??????????????

• ???????????? ?? ???????? ?????????

• ?????????? ?? ????????? ?????????

????????? ?? ????? ??????????????? ??????????????
???? ??????? ??????? ?? ????????? ??? ?????????
???? ?? ????????! ??????? ? size-consistent!
3
????? ?????????
????????? ??????? ? ?????????????????? ???????
?????????? ?? ?????????? ????????????, ? ?????
???? ?? ??????????? ?? ????????? ?? ????????
???????? (????????????)
?????????? ????? ????? ? ??????????? ?? N ? ?
?????? ?? ??????? ???????????!
4
??????? ????????????
????????? ??????? ?? ??????? ???? ?? ???? ??
?????????????? ????- ?/??? ???????????? (CIS,
CID, CISD)
5
??????????
?????????
????
?????
?????? ?????
???????????
????
6
???????? ????? - CAS
7
???????? ????? - CAS
8
????????? ????? - CAS
Total number of active electrons 12 Total
number of active orbitals 10 Number of Alpha
electrons 6 Number of Beta electrons
6 Number of configurations
22155 ............... Enter MCSCF
program ................
?
??????????? ?? ???????
Energy state 1 -227.7807378372 Full
Convergence on CI vector ( 1)
EIGENVALUE -0.22778074E03 (1)0.952
(21)-0.199 (8389)0.079 (8262)-0.072 (2628)-0.061
(8515)-0.060 (8261) 0.059 (8385)-0.056
(2559)-0.056 (10)-0.054 (20)0.048 (9454)-0.046
(15)-0.033 (8458)-0.031 (666)-0.031 (67)-0.030
(6)-0.030 (8009)-0.026 (8330)-0.025 (8328)-0.025
(2632) 0.021 ................
Final one electron symbolic density matrix
1 2 3
4 5 1 0.196131D01 2
-0.561228D-09 0.198043D01 3 -0.543162D-07
-0.207217D-08 0.199636D01 4 0.409563D-07
0.547341D-07 0.117440D-08 0.199805D01 5
0.203391D-07 0.148249D-06 0.862395D-08
-0.429647D-06 0.190156D01 ................ MCSCF
converged. ................
Job cpu time 0 days 0 hours 3 minutes 24.0
seconds
9
????????? ????? - CAS
?
no. active orbitals (n) 4 no. active ELECTRONS
(N) 4 ................ CI Matrix Elements
calculated here
ITN 7 MaxIt 64 E -149.6406596844 DE-8.35D-09
Acc 1.00D-08 Lan 0 ... Do an extra-iteration
for final printing .................
???????? ?????????
Berny optimization. Search for a saddle
point. ................ Eigenvectors required to
have negative eigenvalues CC
CO TH CH HC 1
0.97790 -0.08756 0.09499 0.04098 -0.12645
DI 1 -0.09671
Job cpu time 0 days 0 hours 0 minutes 56.0
seconds
10
????????? ????? - CAS
?
Charge 0 Multiplicity 2 ................ CI
Matrix Elements calculated here NO. OF
CONFIGURATIONS IN REFERENCE SPACE 1
SECONDARY SPACE 8
TERTIARY SPACE
8 NO. OF ORBITALS 3 NO. OF
ELECTRONS 3
ITN 2 MaxIt 64 E -114.9581714848 DE 6.57D-10
Acc 1.00D-08 Lan 0 ... Do an extra-iteration
for final printing ................. Final State
Averaged Density Matrix 1
2 3 1 0.155773D01
2 0.111542D-12 0.103440D01 3
-0.126762D-07 0.109253D-12 0.407864D00 MCSCF
converged. .................
????? ????????? ?????????
State 2 State 1 Energy difference
-0.1026049
Job cpu time 0 days 0 hours 0 minutes 11.0
seconds
11
????????? ????? - CAS
?
Spin-Orbit Integrals for IMat 1 1
2 3 4
5 1 0.00000D00 2 0.00000D00
0.00000D00 3 0.00000D00 0.00000D00
0.00000D00 4 -0.86958D00 -0.40702D00
0.00000D00 0.00000D00 5 0.00000D00
0.00000D00 0.00000D00 -0.10380D02
0.00000D00 .................
ITN 26 MaxIt 64 E -113.7441753492 DE-9.30D-06
Acc 1.00D-05 Lan 0 ... Do an extra-iteration
for final printing .................
Spin-Orbit coupling program.
Number of configs
4 1st state is 1 2nd state is 2 Transition
Spin Density Matrix 1
2 1 0.158944D-12 0.141369D01 2
0.386188D-01-0.158944D-12 Magnitude in
x-direction 0.0 cm-1 Magnitude in
y-direction 0.0 cm-1 Magnitude in
z-direction 63.5 cm-1 Total magnitude
63.5 cm-1 MCSCF converged.
????-????????? ??????????????
Job cpu time 0 days 0 hours 0 minutes 9.0
seconds
12
????????? ????? - CAS
?
State Average Calculation. The weights are
St. 1 w.0.500000 St. 2 w.0.500000
St. .................
ITN 14 MaxIt 64 E -154.0502715533 DE
5.90D-09 Acc 1.00D-08 Lan 0 ... Do an
extra-iteration for final printing ...............
..
??????? ???????
Gradient Difference/Derivative Coupling
Calculation ................. State 2 State
1 Energy difference -0.0004784
Derivative Coupling 0.0012463851
0.1078615792 0.0750725276
-0.0005979612 -0.0548058803
0.0603342678 -0.0012813386
-0.1080059067 -0.0724838793 ................
.
Job cpu time 0 days 0 hours 1 minutes 35.0
seconds
13
???? ?? ?????? ??????????? ? CIS, CID, CISD?

• ?????????? ?? ?????????? (UV/VIS) ??????? - CIS

• ?????? ???????? ?? ????????? ? ??????????

• ?????? ?? ???????? ?? ?????? ??????? ????????????

????????! ??????? ?? ? size-consistent! ?? ??? ??
?????? ???????????.
14
??????? ????????????
CI-?????????????? ?? ?????????? ???? ? ???? ??
??????????? ???????? (??????? ????????????) ?
CAS ??? ...
????????? ??????? ?? ??????? ???? ?? ???? ??
?????????????? ????- ?/??? ???????????? (CIS,
CID, CISD)
15
??????????
16
???????? ?????
17
????????? ????? - CIS
?
SCF Done E(RHF) -113.832890689 A.U. after 12
cycles Convg 0.8267D-08
-V/T 2.0055 S2
0.0000 ................
Range of M.O.s used for correlation 1
34 ................ Compute canonical integrals,
LenV 5932447 ................ E2
-0.3228582560D00 EUMP2 -0.11415574894527D03
................
Max sub-space 200 roots to seek 12 dimension
of matrix 416 Iteration 1 Dimension 12
NMult 12 New state 2 was old state
3 New state 3 was old state 4
Excitation Energies eV at current iteration
Root 1 3.853833375488182 Root 2
8.175076369881843 Root 3
10.843839368958520 ................
??????????? ?? UV ???????
18
????????? ????? - CIS
?
Iteration 8 Dimension 41 NMult 41 Root
1 has converged. Root 2 has
converged. Root 3 has converged.
Excitation Energies eV at current iteration
Root 1 3.700645121660727 Change is
-0.000000000000011 Root 2 7.840807312600316
Change is -0.000000000050180 Root 3
8.767150845777678 Change is -0.000000000458026
Convergence achieved on expansion
vectors. ................
??????????? ?? UV ???????

Excited states from ltAA,BBAA,BBgt singles
matrix
................ Excitation
energies and oscillator strengths Excited State
1 Singlet-A" 3.7006 eV 335.03 nm
f0.0008 8 -gt 9 0.69112 This
state for optimization and/or second-order
correction. Total Energy, E(CIS) -113.696894476
Job cpu time 0 days 0 hours 0 minutes 19.0
seconds
19
????????? ????? - CIS
?
SCF Done E(RHF) -77.5822564013 A.U. after 10
cycles Convg 0.5917D-08
-V/T 1.9556 S2
0.0000 ................ Range of M.O.s used for
correlation 3 46 ................ Excitati
on energies and oscillator strengths Excited
State 1 Singlet-B3U 10.2782 eV 120.63 nm
f0.1487 8 -gt 10 0.63635 8
-gt 15 -0.28983 This state for
optimization and/or second-order correction.
Total Energy, E(CIS) -77.2045409041 ...........
..... Excited State 5 Singlet-B2G 11.1389
eV 111.31 nm f0.0000 8 -gt 9
0.68323 8 -gt 16 -0.16667 The
selected state is a singlet
?????? ????????? ?????????
Job cpu time 0 days 0 hours 0 minutes 34.0
seconds
20
????????? ????? - CID
?
SCF Done E(RHF) -75.9076402329 A.U. after
10 cycles Convg 0.1868D-08
-V/T 1.9992 S2
0.0000 ................. Range of M.O.s used for
correlation 2 13 ................. Configu
ration Interaction with double substitutions
Ite
rations 50 Convergence 0.100D-06 Normalization
A(0)1 .................
DE(CI) -0.12835619D00 E(CI)
-0.76035996424D02 NORM(A) 0.10191013D01 SIZE-
CONSISTENCY CORRECTION S.C.C.
-0.37846940D-02 E(CI,SIZE)
-0.76039781129D02 .................
???? ?????? ???????????
Job cpu time 0 days 0 hours 0 minutes 8.0
seconds
21
????????? ????? - CISD
?
SCF Done E(RHF) -75.5858125135 A.U. after 10
cycles Convg 0.5361D-09
-V/T 2.0018 S2
0.0000 ................. Range of M.O.s used for
correlation 2 13 ................. Configu
ration Interaction with single- and double
substitutions
.................
DE(CI) -0.12384256D00 E(CI)
-0.75709655078D02 NORM(A) 0.10172438D01 SIZE-
CONSISTENCY CORRECTION S.C.C. -0.32872965D-02
E(CI,SIZE) -0.75712942060D02 ............
.....
???????? ? ?????? ???????????
Job cpu time 0 days 0 hours 0 minutes 7.0
seconds
22
???? ? ?????????????? ????????
DE0.194 a.u. 121.87 kcal/mol
?
E(RHF) -76.00986871 a.u. E(CID) -76.20407800
a.u. E(CISD) -76.20482031 a.u. E(CAS(10,10))
-76.14092635 a.u.
DE0.001 a.u. 0.47 kcal/mol
?
?
DE-0.064 a.u. -40.09 kcal/mol
E(MP2) -76.19598795 a.u.
23
GVB-??????
????? ??????? ??? ?????????? ?? ????????? ???
?????? ?? ?????????? ??????. ???????? ?? ?????
???? ???????????? ???????? ?? ??????????
???????? ???????????? ????? ??????? ?????? ???
?????????? ?????????? ??????
24
GVB-??????
GVB(Npair2)/6-31g(d) guess(lowsym,read) ......
........... 1 4 0 2 3 9 2 2
???????????? ????? ??? GVB ???????????? ?
???????????? ?? ????????? ??!
25
GVB-??????
There are 9 symmetry adapted basis functions of
A1 symmetry. There are 1 symmetry adapted basis
functions of A2 symmetry. There are 3 symmetry
adapted basis functions of B1 symmetry. There
are 5 symmetry adapted basis functions of B2
symmetry .................. Separated pair
information Pair NOrb Root
Coefficient(Orbital) 1 2 1
0.900000( 3) -0.100000( 5) 2 2 1
0.900000( 2) -0.100000( 6) ................. Co
nfiguration Interaction with single- and double
substitutions OCBSE shell sequence 1 2 3 4
5 6 Shell Orbitals 1 1 2 4
7 3 3 4 5 5 2 6
6 ................. Generalized SCF program
final output FINAL ENERGIES FOR THIS RUN
ELECTRONIC ENERGY......... -45.1045643205
NUCLEAR REPULSION ENERGY.. 6.1626362067
TOTAL ENERGY.............. -38.9419281138
SQCDF 0.196D-10 CONVERGENCE CRITERION
0.100D-09 ITERATION NO 1 MAX NO
ITERATIONS 64
26
????????????? ??????

• ????????? ?????????? 9.2 ? 9.6().
• ??????????? RCIS/6-31G UV-????????? ?? ?? ?
  ???-???????? ? ?? ????????.
• () ??????? ????????? ?? ????????? ????????? (?
  ?????????????? ???????) ?? ?? ? ???-???????? ?
  CISD/6-31G ? CASSCF/6-31G, ???? ?????????
  ??????? ???????????? ????????? ?????????? RHF ??.