Symmetry of EOM-EE(EA)-CCSD

Questions
#1

Hello,
I’m new to qchem and I’m using 4.4 version in my lab.

I used mixed basis set for phenoxide to perform EOM-EE-CCSD.
After optimizing the penoxide at first, I checked the C2V symmetry and then turned the EOM calculation.

But
-EE_SINGLETS:
Inconsistent with the number of irreps in the molecule.
word came up.

The INPUT FILE I wrote is:

$molecule
-1 1
C 0.0000000 1.2151483 0.2410758
C 0.0000000 1.2041023 -1.1514372
C -0.0000000 0.0000000 1.0315022
C -0.0000000 -1.2151483 0.2410758
C -0.0000000 -1.2041023 -1.1514372
C 0.0000000 -0.0000000 -1.8807141
O -0.0000000 0.0000000 2.3055113
H 0.0000000 2.1625467 0.7878091
H 0.0000000 2.1578043 -1.6915752
H -0.0000000 -2.1625467 0.7878091
H -0.0000000 -2.1578043 -1.6915752
H 0.0000000 -0.0000000 -2.9727272
$end

$rem
BASIS = Mixed
EE_SINGLETS = [0,0,1,0]
GUI = 2
METHOD = EOM-CCSD
$end

$basis
C 1
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000

C 2
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000

C 3
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000

C 4
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000

C 5
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000

C 6
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000

O 7
aug-cc-pVDZ

H 8
aug-cc-pVDZ

H 9
aug-cc-pVDZ

H 10
aug-cc-pVDZ

H 11
aug-cc-pVDZ

H 12
aug-cc-pVDZ

$end

What is the problem?

#2

Using BASIS=MIXED causes Q-Chem to disable point group symmetry because different atoms in positions related by symmetry can potentially be assigned different basis sets thus breaking the symmetry. With point group symmetry disabled, EE_STATES=[0,0,1,0] becomes an invalid specification.

If using a basis that break molecular symmetry is necessary, then the EE_STATES keyword must be adjusted for C1 point group, for example EE_STATES=[4].

In your case, however, the atoms in the molecule are not assigned different basis sets. Therefore, it is possible to use BASIS=GEN, which assigns basis set on the per-element basis and does not turn symmetry off.

$molecule
-1 1
C 0.0000000 1.2151483 0.2410758
C 0.0000000 1.2041023 -1.1514372
C -0.0000000 0.0000000 1.0315022
C -0.0000000 -1.2151483 0.2410758
C -0.0000000 -1.2041023 -1.1514372
C 0.0000000 -0.0000000 -1.8807141
O -0.0000000 0.0000000 2.3055113
H 0.0000000 2.1625467 0.7878091
H 0.0000000 2.1578043 -1.6915752
H -0.0000000 -2.1625467 0.7878091
H -0.0000000 -2.1578043 -1.6915752
H 0.0000000 -0.0000000 -2.9727272
$end

$rem
!BASIS = Mixed
basis = gen
EE_SINGLETS = [0,0,1,0]
GUI = 2
METHOD = EOM-CCSD
$end

$basis
C 0
S 9 1.00
6.665000D+03 6.920000D-04
1.000000D+03 5.329000D-03
2.280000D+02 2.707700D-02
6.471000D+01 1.017180D-01
2.106000D+01 2.747400D-01
7.495000D+00 4.485640D-01
2.797000D+00 2.850740D-01
5.215000D-01 1.520400D-02
1.596000D-01 -3.191000D-03
S 9 1.00
6.665000D+03 -1.460000D-04
1.000000D+03 -1.154000D-03
2.280000D+02 -5.725000D-03
6.471000D+01 -2.331200D-02
2.106000D+01 -6.395500D-02
7.495000D+00 -1.499810D-01
2.797000D+00 -1.272620D-01
5.215000D-01 5.445290D-01
1.596000D-01 5.804960D-01
S 1 1.00
1.596000D-01 1.000000D+00
S 1 1.00
0.0469000 1.0000000
P 4 1.00
9.439000D+00 3.810900D-02
2.002000D+00 2.094800D-01
5.456000D-01 5.085570D-01
1.517000D-01 4.688420D-01
P 1 1.00
1.517000D-01 1.000000D+00
P 1 1.00
0.0404100 1.0000000
D 1 1.00
5.500000D-01 1.0000000
D 1 1.00
0.1510000 1.0000000
S 1 1.00
1.37820E-2 1.0000000
S 1 1.00
4.04998E-3 1.0000000
S 1 1.00
1.19013E-3 1.0000000
S 1 1.00
3.4973E-4 1.0000000
S 1 1.00
1.02771E-04 1.0000000
S 1 1.00
3.02004E-05 1.0000000
S 1 1.00
8.87468E-06 1.0000000
****
O 0
aug-cc-pVDZ
****
H 0
aug-cc-pVDZ
****
$end
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