Re: question about the output of state average of casscf on gaussian

dummy@example.com (sobereva) — Fri, 07 Feb 2025 19:50:39 +0000

You calculated S0, S1 and S2. The three EIGENVALUE values correspond to energy of the three states.

question about the output of state average of casscf on gaussian

dummy@example.com (choconostle123) — Fri, 07 Feb 2025 18:10:14 +0000

Hello, I am learning about how to calculate excited states using CASSCF in Gaussian, but I have some doubts about the excitation energy in the output.

I performed a calculation for the formaldehyde molecule with stateaverage . The input is as follows:

#p cas(4,3,NRoot=3,StateAverage) def2tzvp

Title Card Required

0 1
C -0.00001600 0.52685200 0.00000000
H 0.92907900 1.09677600 0.00000000
H -0.92885800 1.09725000 0.00000000
O -0.00001600 -0.66939200 0.00000000

0.3333 0.3333 0.3333

However, in the output, I don't know where the excitation energy is :S.

Are the eigenvalues the energies of the ground state and the 2 excited states?

I am sharing the output below.

-----------------------------------------
#p cas(4,3,NRoot=3,StateAverage) def2tzvp
-----------------------------------------
1/38=1/1;
2/12=2,17=6,18=5,40=1/2;
3/5=44,7=101,16=1,25=1,32=1,116=101/1,2,3;
4/17=4,18=3/1,5;
5/5=2,17=11000000,28=3,38=5/10;
6/7=2,8=2,9=2,10=2,28=1/1;
99/5=1,9=1/99;
Leave Link 1 at Fri Feb 07 11:51:36 2025, MaxMem= 0 cpu: 0.0
(Enter C:\G09W\l101.exe)
-------------------
Title Card Required
-------------------
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
C -0.00002 0.52685 0.
H 0.92908 1.09678 0.
H -0.92886 1.09725 0.
O -0.00002 -0.66939 0.

NAtoms= 4 NQM= 4 NQMF= 0 NMMI= 0 NMMIF= 0
NMic= 0 NMicF= 0.
Isotopes and Nuclear Properties:
(Nuclear quadrupole moments (NQMom) in fm**2, nuclear magnetic moments (NMagM)
in nuclear magnetons)

Atom 1 2 3 4
IAtWgt= 12 1 1 16
AtmWgt= 12.0000000 1.0078250 1.0078250 15.9949146
NucSpn= 0 1 1 0
AtZEff= 0.0000000 0.0000000 0.0000000 0.0000000
NQMom= 0.0000000 0.0000000 0.0000000 0.0000000
NMagM= 0.0000000 2.7928460 2.7928460 0.0000000
AtZNuc= 6.0000000 1.0000000 1.0000000 8.0000000
Leave Link 101 at Fri Feb 07 11:51:36 2025, MaxMem= 33554432 cpu: 0.0
(Enter C:\G09W\l202.exe)
Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.000016 0.526852 0.000000
2 1 0 0.929079 1.096776 0.000000
3 1 0 -0.928858 1.097250 0.000000
4 8 0 -0.000016 -0.669392 0.000000
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4
1 C 0.000000
2 H 1.089968 0.000000
3 H 1.090001 1.857937 0.000000
4 O 1.196244 1.995637 1.995939 0.000000
Stoichiometry CH2O
Framework group CS[SG(CH2O)]
Deg. of freedom 5
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.000016 -0.526852 0.000000
2 1 0 0.929079 -1.096776 0.000000
3 1 0 -0.928858 -1.097250 0.000000
4 8 0 -0.000016 0.669392 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 290.5360811 39.5870535 34.8399315
Leave Link 202 at Fri Feb 07 11:51:36 2025, MaxMem= 33554432 cpu: 0.0
(Enter C:\G09W\l301.exe)
Standard basis: def2TZVP (5D, 7F)
Ernie: Thresh= 0.10000D-02 Tol= 0.10000D-05 Strict=F.
There are 60 symmetry adapted cartesian basis functions of A' symmetry.
There are 24 symmetry adapted cartesian basis functions of A" symmetry.
There are 52 symmetry adapted basis functions of A' symmetry.
There are 22 symmetry adapted basis functions of A" symmetry.
74 basis functions, 118 primitive gaussians, 84 cartesian basis functions
8 alpha electrons 8 beta electrons
nuclear repulsion energy 31.5866087459 Hartrees.
IExCor= 0 DFT=F Ex=HF Corr=None ExCW=0 ScaHFX= 1.000000
ScaDFX= 1.000000 1.000000 1.000000 1.000000 ScalE2= 1.000000 1.000000
IRadAn= 0 IRanWt= -1 IRanGd= 0 ICorTp=0 IEmpDi= 4
NAtoms= 4 NActive= 4 NUniq= 4 SFac= 1.00D+00 NAtFMM= 60 NAOKFM=F Big=F
Integral buffers will be 262144 words long.
Regular integral format.
Two-electron integral symmetry is turned off.
Leave Link 301 at Fri Feb 07 11:51:36 2025, MaxMem= 33554432 cpu: 0.0
(Enter C:\G09W\l302.exe)
NPDir=0 NMtPBC= 1 NCelOv= 1 NCel= 1 NClECP= 1 NCelD= 1
NCelK= 1 NCelE2= 1 NClLst= 1 CellRange= 0.0.
One-electron integrals computed using PRISM.
1 Symmetry operations used in ECPInt.
ECPInt: NShTT= 465 NPrTT= 1428 LenC2= 466 LenP2D= 1323.
LDataN: DoStor=T MaxTD1= 6 Len= 172
The smallest eigenvalue of the overlap matrix is 1.414D-03
NBasis= 74 RedAO= F EigKep= 0.00D+00 NBF= 52 22
NBsUse= 74 1.00D-04 EigRej= 0.00D+00 NBFU= 52 22
Leave Link 302 at Fri Feb 07 11:51:36 2025, MaxMem= 33554432 cpu: 0.0
(Enter C:\G09W\l303.exe)
DipDrv: MaxL=1.
Leave Link 303 at Fri Feb 07 11:51:36 2025, MaxMem= 33554432 cpu: 0.0
(Enter C:\G09W\l401.exe)
ExpMin= 9.52D-02 ExpMax= 2.70D+04 ExpMxC= 9.22D+02 IAcc=2 IRadAn= 4 AccDes= 0.00D+00
Harris functional with IExCor= 205 and IRadAn= 4 diagonalized for initial guess.
HarFok: IExCor= 205 AccDes= 0.00D+00 IRadAn= 4 IDoV= 1 UseB2=F ITyADJ=14
ICtDFT= 3500011 ScaDFX= 1.000000 1.000000 1.000000 1.000000
FoFCou: FMM=F IPFlag= 0 FMFlag= 100000 FMFlg1= 0
NFxFlg= 0 DoJE=T BraDBF=F KetDBF=T FulRan=T
wScrn= 0.000000 ICntrl= 500 IOpCl= 0 I1Cent= 200000004 NGrid= 0
NMat0= 1 NMatS0= 1 NMatT0= 0 NMatD0= 1 NMtDS0= 0 NMtDT0= 0
Petite list used in FoFCou.
Harris En= -113.998494491141
JPrj=0 DoOrth=F DoCkMO=F.
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A") (A')
Virtual (A") (A') (A') (A') (A") (A') (A') (A') (A') (A')
(A') (A") (A") (A') (A') (A") (A') (A') (A') (A')
(A") (A") (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A') (A") (A")
(A') (A') (A") (A') (A") (A') (A") (A') (A') (A')
(A') (A') (A") (A') (A") (A') (A") (A') (A") (A')
(A') (A") (A') (A') (A') (A')
The electronic state of the initial guess is 1-A'.
Leave Link 401 at Fri Feb 07 11:51:36 2025, MaxMem= 33554432 cpu: 0.0
(Enter C:\G09W\l405.exe)
Truncation Level= 99999
a= 2 b= 0 c= 1
a=N/2 - s b=2s c=n- (a+b)
no. active orbitals (n) 3
no. active ELECTRONS (N)= 4
IRREPS TO BE RETAINED = 1 2
GROUP IRREP. MULT. TABLE
1 2
2 1
IRREP. LABELS FOR ORBITALS
2 1 2
BOTTOM WEIGHT= 6 TOP WEIGHT= 10
Configuration 1 Symmetry 1 110
Configuration 2 Symmetry 2 1ab
Configuration 3 Symmetry 1 101
Configuration 4 Symmetry 1 a1b
Configuration 5 Symmetry 2 ab1
Configuration 6 Symmetry 1 011
NO OF BASIS FUNCTIONS = 6 NO TO BE DELETED = 0
CI Matrix Elements calculated here
NO. OF CONFIGURATIONS IN REFERENCE SPACE = 1
SECONDARY SPACE = 6
TERTIARY SPACE = 6
NO. OF ORBITALS = 3
NO. OF ELECTRONS = 4
NO. OF WEIGHTS = 5
REFERENCE STATE CONFIGURATIONS ARE: 0
NO. OF CORE ORBITALS = 0
OPTION: NON-DIAGONAL HOLE LINE INTERACTIONS INCLUDED
Len28= 512 LenMCI= 241.
Leave Link 405 at Fri Feb 07 11:51:37 2025, MaxMem= 33554432 cpu: 1.0
(Enter C:\G09W\l510.exe)
Enter MCSCF program.
NO. OF ORBITALS = 74 NO. OF CORE-ORBITALS = 6
NO. OF VALENCE-ORBITALS = 3 NO. OF VIRTUAL-ORBITALS = 65
USED ACCURACY IN CHECKING CONVERGENCE = 1.00D-08
Memory needed for Incore Integrals: 7057107
Integrals KEPT IN MEMORY
IBUJAK length= 49980
Integral file not found: evaluate integrals
FoFCou: FMM=F IPFlag= 0 FMFlag= 0 FMFlg1= 0
NFxFlg= 0 DoJE=F BraDBF=F KetDBF=F FulRan=T
wScrn= 0.000000 ICntrl= 600 IOpCl= 0 I1Cent= 0 NGrid= 0
NMat0= 1 NMatS0= 1 NMatT0= 0 NMatD0= 1 NMtDS0= 0 NMtDT0= 0
Symmetry not used in FoFCou.
Defining IBUGAM
State Average Calculation. The weights are:
St.: 1 w.=0.333300 # St.: 2 w.=0.333300 # St.: 3 w.=0.333300 # St.:
2ND ORD PT ENERGY CV -0.004048 CU -0.048133 UV -0.040641
TOTAL -113.503472
ITN= 1 MaxIt= 64 E= -113.4106496306 DE=-1.13D+02 Acc= 1.00D-08 Lan= 0
ITN= 2 MaxIt= 64 E= -113.4944047782 DE=-8.38D-02 Acc= 1.00D-08 Lan= 0
ITN= 3 MaxIt= 64 E= -113.5020463877 DE=-7.64D-03 Acc= 1.00D-08 Lan= 0
ITN= 4 MaxIt= 64 E= -113.5089633540 DE=-6.92D-03 Acc= 1.00D-08 Lan= 0
ITN= 5 MaxIt= 64 E= -113.5068700003 DE= 2.09D-03 Acc= 1.00D-08 Lan= 0
ITN= 6 MaxIt= 64 E= -113.5081119793 DE=-1.24D-03 Acc= 1.00D-08 Lan= 0
ITN= 7 MaxIt= 64 E= -113.5074656605 DE= 6.46D-04 Acc= 1.00D-08 Lan= 0
ITN= 8 MaxIt= 64 E= -113.5076941123 DE=-2.28D-04 Acc= 1.00D-08 Lan= 0
ITN= 9 MaxIt= 64 E= -113.5075431541 DE= 1.51D-04 Acc= 1.00D-08 Lan= 0
ITN= 10 MaxIt= 64 E= -113.5075816620 DE=-3.85D-05 Acc= 1.00D-08 Lan= 0
ITN= 11 MaxIt= 64 E= -113.5075484014 DE= 3.33D-05 Acc= 1.00D-08 Lan= 0
ITN= 12 MaxIt= 64 E= -113.5075542665 DE=-5.87D-06 Acc= 1.00D-08 Lan= 0
ITN= 13 MaxIt= 64 E= -113.5075470663 DE= 7.20D-06 Acc= 1.00D-08 Lan= 0
ITN= 14 MaxIt= 64 E= -113.5075478623 DE=-7.96D-07 Acc= 1.00D-08 Lan= 0
ITN= 15 MaxIt= 64 E= -113.5075463471 DE= 1.52D-06 Acc= 1.00D-08 Lan= 0
ITN= 16 MaxIt= 64 E= -113.5075464600 DE=-1.13D-07 Acc= 1.00D-08 Lan= 0
ITN= 17 MaxIt= 64 E= -113.5075461684 DE= 2.92D-07 Acc= 1.00D-08 Lan= 0
ITN= 18 MaxIt= 64 E= -113.5075462023 DE=-3.38D-08 Acc= 1.00D-08 Lan= 0
ITN= 19 MaxIt= 64 E= -113.5075461614 DE= 4.09D-08 Acc= 1.00D-08 Lan= 0
ITN= 20 MaxIt= 64 E= -113.5075461812 DE=-1.98D-08 Acc= 1.00D-08 Lan= 0
ITN= 21 MaxIt= 64 E= -113.5075461839 DE=-2.73D-09 Acc= 1.00D-08 Lan= 0
... Do an extra-iteration for final printing.

EIGENVALUES AND EIGENVECTORS OF CI MATRIX

( 1) EIGENVALUE -113.9372546122
( 1) 0.8721303 ( 4)-0.4842478 ( 6)-0.0681868 ( 3)-0.0156029 ( 2) 0.0000000 ( 5) 0.0000000 (

( 2) EIGENVALUE -113.7834088173
( 2) 0.9999588 ( 5) 0.0090727 ( 4) 0.0000000 ( 1) 0.0000000 ( 3) 0.0000000 ( 6) 0.0000000 (

( 3) EIGENVALUE -113.5075461955
( 4) 0.8726403 ( 1) 0.4822660 ( 3) 0.0634586 ( 6)-0.0434911 ( 2) 0.0000000 ( 5) 0.0000000 (
Final one electron symbolic density matrix:
1 2 3
1 0.123472D+01
2 -0.284709D-12 0.199195D+01
3 -0.108298D+01 -0.182632D-12 0.773338D+00
MCSCF converged.
Leave Link 510 at Fri Feb 07 11:51:45 2025, MaxMem= 33554432 cpu: 8.0
(Enter C:\G09W\l601.exe)
Copying SCF densities to generalized density rwf, IOpCl= 0 IROHF=3.

**********************************************************************

Population analysis using the SCF density.

**********************************************************************

Orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A") (A')
Virtual (A") (A') (A') (A') (A") (A') (A') (A') (A') (A')
(A') (A") (A") (A') (A') (A") (A') (A') (A') (A')
(A") (A") (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A') (A") (A")
(A') (A') (A") (A') (A") (A') (A") (A') (A') (A')
(A') (A') (A") (A') (A") (A') (A") (A') (A") (A')
(A') (A") (A') (A') (A') (A')
The electronic state is 1-A'.
Alpha occ. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha occ. eigenvalues -- 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000 0.00000 0.00000 0.00000 0.00000
Alpha virt. eigenvalues -- 0.00000
Condensed to atoms (all electrons):
1 2 3 4
1 C 4.810169 0.414962 0.414913 0.002124
2 H 0.414962 0.604744 -0.075572 -0.057680
3 H 0.414913 -0.075572 0.604694 -0.057628
4 O 0.002124 -0.057680 -0.057628 8.698157
Mulliken charges:
1
1 C 0.357833
2 H 0.113546
3 H 0.113593
4 O -0.584972
Sum of Mulliken charges = 0.00000
Mulliken charges with hydrogens summed into heavy atoms:
1
1 C 0.584972
4 O -0.584972
Electronic spatial extent (au): = 61.1733
Charge= 0.0000 electrons
Dipole moment (field-independent basis, Debye):
X= -0.0001 Y= -3.2032 Z= 0.0000 Tot= 3.2032
Quadrupole moment (field-independent basis, Debye-Ang):
XX= -11.4588 YY= -13.8208 ZZ= -11.9322
XY= 0.0006 XZ= 0.0000 YZ= 0.0000
Traceless Quadrupole moment (field-independent basis, Debye-Ang):
XX= 0.9451 YY= -1.4169 ZZ= 0.4717
XY= 0.0006 XZ= 0.0000 YZ= 0.0000
Octapole moment (field-independent basis, Debye-Ang**2):
XXX= 0.0004 YYY= 0.3317 ZZZ= 0.0000 XYY= -0.0009
XXY= -0.4736 XXZ= 0.0000 XZZ= 0.0000 YZZ= 1.4023
YYZ= 0.0000 XYZ= 0.0000
Hexadecapole moment (field-independent basis, Debye-Ang**3):
XXXX= -17.5288 YYYY= -47.7035 ZZZZ= -12.4956 XXXY= -0.0001
XXXZ= 0.0000 YYYX= 0.0017 YYYZ= 0.0000 ZZZX= 0.0000
ZZZY= 0.0000 XXYY= -10.1164 XXZZ= -5.3572 YYZZ= -11.0727