Ceilidh ... Re: MCSCF CALCULATIONS OF ACETILENE + O3

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Re: MCSCF CALCULATIONS OF ACETILENE + O3

Probably, the problem is in what you found in your question #2. The warning you see means linear dependence of the basis set. This frequently happens with diffuse bases. Set $CONTRL INTTYP=HONDO ITOL=30 ICUT=10 $END, this may help. If not, you'll have to drop some diffuse basis functions as stated in the WARNING.

Also set $MCSCF ACURCY=1.0E-06 ENGTOL=1.0E-12 $END and MOREAD all orbitals rather than occupied only (that is, add $VEC group from PUNCH marked with "OPTIMIZED ORBITALS" rather than "NATURAL ORBITALS".

In addition, the active space seems somewhat inadequate, IMHO. Some CASSCF natural orbitals have occupations ~1.99 and ~0.01. This means that they anly slightly contribute to the CASSCF wavefunction. Probably, you should include some other orbitals instead of them.

On Sat Oct 29 '11 1:39pm, Alex Maiorov wrote
--------------------------------------------
>Hello, everybody
>I perform MCSCF(14,11)/aug-cc-pvdz calculations of reaction c2h2(acetylene)+O3(ozone)

>I have two questions:
>1) At this calculations, i have vectors converged, but during thirst step
>of calculations hessian or thirst step of nseach i have vectors scf inconverged.
>I changed the initial geometry, but with this reagents the problem remains.
>
>
>2) All my calculations with firefly in aug-cc-pvdz gives me always warning,
>i tried to change input file as it was written in warning, but it didnot helped

> * * * WARNING * * *
> ------------------------------------------------------------------------------
> THE OVERLAP MATRIX HAS 1 EIGENVALUES BELOW 1.0E-05.
> THE SMALLEST OF THESE IS 3.02892E-06.
> THIS INDICATES A PARTIAL LINEAR DEPENDENCE IN YOUR ATOMIC BASIS.

> TO OBTAIN SCF CONVERGENCE MAY REQUIRE
> MORE ACCURATE INTEGRAL EVALUATION (INTTYP=HONDO, ICUT=11, ITOL=30 IN $CONTRL),
> MORE ACCURATE DIRECT SCF FOCK MATRIX FORMATION (FDIFF=.FALSE. IN $SCF), OR
> CHANGING CONVERGERS (DIIS=.T. SOSCF=.F. IN $SCF).

> EIGENVALUES BELOW 1.0D-07 PROBABLY WON'T CONVERGE.
> EIGENVALUES BETWEEN 1.0D-07 AND 1.0D-06 MAY REQUIRE
> LOOSENING OF -NCONV- DENSITY CONVERGENCE IN $SCF.

> THE OVERALL DEGREES OF AOS LINEAR INDEPENDENCE ARE:
> 0.6754 - O 7 XZ, SHELL 52, AO 132
> 0.6753 - O 5 XZ, SHELL 34, AO 82
> 0.6580 - O 6 XZ, SHELL 43, AO 107
> 0.6529 - C 2 XZ, SHELL 15, AO 39
> 0.6526 - C 1 XZ, SHELL 6, AO 14
> 0.6450 - O 7 Z, SHELL 50, AO 124
> 0.6447 - O 5 Z, SHELL 32, AO 74
> 0.6375 - O 5 YZ, SHELL 34, AO 83
> 0.6371 - O 7 YZ, SHELL 52, AO 133
> 0.6231 - O 5 XY, SHELL 34, AO 81
> 0.6225 - O 7 XY, SHELL 52, AO 131
> 0.6165 - O 6 XY, SHELL 43, AO 106
> 0.6014 - O 6 X, SHELL 41, AO 97
> 0.5958 - O 6 Z, SHELL 41, AO 99
> 0.5917 - O 6 YZ, SHELL 43, AO 108
> 0.5815 - O 5 X, SHELL 32, AO 72
> 0.5812 - O 7 X, SHELL 50, AO 122
> 0.5529 - O 5 Y, SHELL 32, AO 73
> 0.5523 - O 7 Y, SHELL 50, AO 123
> 0.5406 - C 2 Z, SHELL 13, AO 31
> 0.5405 - C 1 Z, SHELL 4, AO 6
> 0.5309 - H 3 Z, SHELL 21, AO 55
> 0.5309 - H 4 Z, SHELL 26, AO 64
> 0.4964 - O 6 Y, SHELL 41, AO 98
> 0.4358 - C 2 X, SHELL 13, AO 29
> 0.4355 - C 1 X, SHELL 4, AO 4
> 0.4147 - H 3 X, SHELL 21, AO 53
> 0.4143 - H 4 X, SHELL 26, AO 62
> 0.3583 - C 1 YZ, SHELL 6, AO 15
> 0.3583 - C 2 YZ, SHELL 15, AO 40
> 0.2656 - C 2 XY, SHELL 15, AO 38
> 0.2647 - C 1 XY, SHELL 6, AO 13
> 0.1803 - C 1 Y, SHELL 4, AO 5
> 0.1803 - C 2 Y, SHELL 13, AO 30
> 0.1718 - O 7 XZ, SHELL 55, AO 142
> 0.1712 - O 5 XZ, SHELL 37, AO 92
> 0.1522 - C 2 XZ, SHELL 18, AO 49
> 0.1513 - H 4 Y, SHELL 26, AO 63
> 0.1512 - H 3 Y, SHELL 21, AO 54
> 0.1510 - C 1 XZ, SHELL 9, AO 24
> 0.1465 - O 5 ZZ, SHELL 34, AO 80
> 0.1465 - O 7 ZZ, SHELL 52, AO 130
> 0.1464 - O 5 XX, SHELL 34, AO 78
> 0.1464 - O 7 XX, SHELL 52, AO 128
> 0.1462 - O 5 YY, SHELL 34, AO 79
> 0.1462 - O 7 YY, SHELL 52, AO 129
> 0.1426 - O 6 ZZ, SHELL 43, AO 105
> 0.1422 - O 6 YY, SHELL 43, AO 104
> 0.1413 - O 6 XX, SHELL 43, AO 103
> 0.1211 - C 1 XX, SHELL 6, AO 10
> 0.1211 - C 2 XX, SHELL 15, AO 35
> 0.1134 - C 1 ZZ, SHELL 6, AO 12
> 0.1134 - C 2 ZZ, SHELL 15, AO 37
> 0.8369E-01 - O 5 S, SHELL 29, AO 69
> 0.8360E-01 - O 7 S, SHELL 47, AO 119
> 0.8166E-01 - O 6 XZ, SHELL 46, AO 117
> 0.7582E-01 - O 6 S, SHELL 38, AO 94
> 0.7486E-01 - H 4 S, SHELL 24, AO 60
> 0.7486E-01 - H 3 S, SHELL 19, AO 51
> 0.6889E-01 - O 5 XY, SHELL 37, AO 91
> 0.6824E-01 - O 7 XY, SHELL 55, AO 141
> 0.6484E-01 - C 1 S, SHELL 1, AO 1
> 0.6484E-01 - C 2 S, SHELL 10, AO 26
> 0.5191E-01 - C 2 Z, SHELL 17, AO 44
> 0.5186E-01 - C 1 Z, SHELL 8, AO 19
> 0.4261E-01 - O 5 YZ, SHELL 37, AO 93
> 0.4245E-01 - O 7 YZ, SHELL 55, AO 143
> 0.3909E-01 - O 5 S, SHELL 30, AO 70
> 0.3904E-01 - O 7 S, SHELL 48, AO 120
> 0.3574E-01 - C 1 YY, SHELL 6, AO 11
> 0.3572E-01 - C 2 YY, SHELL 15, AO 36
> 0.3516E-01 - O 6 S, SHELL 39, AO 95
> 0.3167E-01 - O 7 Z, SHELL 54, AO 137
> 0.3159E-01 - O 5 Z, SHELL 36, AO 87
> 0.3140E-01 - O 6 XY, SHELL 46, AO 116
> 0.3101E-01 - O 6 X, SHELL 45, AO 110
> 0.2957E-01 - O 5 XX, SHELL 37, AO 88
> 0.2949E-01 - O 7 XX, SHELL 55, AO 138
> 0.2852E-01 - C 1 S, SHELL 2, AO 2
> 0.2852E-01 - C 2 S, SHELL 11, AO 27
> 0.2780E-01 - O 7 ZZ, SHELL 55, AO 140
> 0.2779E-01 - H 3 Z, SHELL 23, AO 59
> 0.2778E-01 - O 5 ZZ, SHELL 37, AO 90
> 0.2778E-01 - H 4 Z, SHELL 28, AO 68
> 0.2522E-01 - O 6 XX, SHELL 46, AO 113
> 0.2246E-01 - O 6 Z, SHELL 45, AO 112
> 0.2046E-01 - O 5 X, SHELL 36, AO 85
> 0.2033E-01 - O 7 X, SHELL 54, AO 135
> 0.1933E-01 - O 6 YZ, SHELL 46, AO 118
> 0.1902E-01 - O 6 ZZ, SHELL 46, AO 115
> 0.1712E-01 - O 5 X, SHELL 33, AO 75
> 0.1693E-01 - O 7 X, SHELL 51, AO 125
> 0.1530E-01 - H 3 X, SHELL 23, AO 57
> 0.1528E-01 - H 4 X, SHELL 28, AO 66
> 0.1519E-01 - O 5 Y, SHELL 36, AO 86
> 0.1504E-01 - O 7 Y, SHELL 54, AO 136
> 0.1233E-01 - C 2 X, SHELL 17, AO 42
> 0.1225E-01 - C 1 X, SHELL 8, AO 17
> 0.1059E-01 - O 5 YY, SHELL 37, AO 89
> 0.1042E-01 - O 7 YY, SHELL 55, AO 139
> 0.1037E-01 - O 5 Z, SHELL 33, AO 77
> 0.1033E-01 - O 7 Z, SHELL 51, AO 127
> 0.9583E-02 - O 6 X, SHELL 42, AO 100
> 0.7646E-02 - C 1 YZ, SHELL 9, AO 25
> 0.7646E-02 - C 2 YZ, SHELL 18, AO 50
> 0.7448E-02 - C 2 ZZ, SHELL 18, AO 47
> 0.7448E-02 - C 1 ZZ, SHELL 9, AO 22
> 0.6997E-02 - C 2 XX, SHELL 18, AO 45
> 0.6986E-02 - C 1 XX, SHELL 9, AO 20
> 0.6895E-02 - O 6 YY, SHELL 46, AO 114
> 0.5378E-02 - C 1 Z, SHELL 5, AO 9
> 0.5377E-02 - C 2 Z, SHELL 14, AO 34
> 0.5374E-02 - O 6 Z, SHELL 42, AO 102
> 0.4920E-02 - O 6 Y, SHELL 45, AO 111
> 0.4521E-02 - C 1 XY, SHELL 9, AO 23
> 0.4517E-02 - C 2 XY, SHELL 18, AO 48
> 0.4355E-02 - H 4 Y, SHELL 28, AO 67
> 0.4355E-02 - H 3 Y, SHELL 23, AO 58
> 0.3180E-02 - O 5 Y, SHELL 33, AO 76
> 0.3108E-02 - O 7 Y, SHELL 51, AO 126
> 0.2609E-02 - H 3 S, SHELL 22, AO 56
> 0.2609E-02 - H 4 S, SHELL 27, AO 65
> 0.2582E-02 - C 2 X, SHELL 14, AO 32
> 0.2575E-02 - C 1 X, SHELL 5, AO 7
> 0.2190E-02 - O 5 S, SHELL 31, AO 71
> 0.2151E-02 - O 7 S, SHELL 49, AO 121
> 0.1463E-02 - O 6 Y, SHELL 42, AO 101
> 0.1458E-02 - O 6 S, SHELL 40, AO 96
> 0.1404E-02 - O 5 S, SHELL 35, AO 84
> 0.1392E-02 - O 7 S, SHELL 53, AO 134
> 0.1026E-02 - O 6 S, SHELL 44, AO 109
> 0.6838E-03 - C 1 Y, SHELL 8, AO 18
> 0.6836E-03 - C 2 Y, SHELL 17, AO 43
> 0.3763E-03 - H 3 S, SHELL 20, AO 52
> 0.3762E-03 - H 4 S, SHELL 25, AO 61
> 0.1805E-03 - C 2 YY, SHELL 18, AO 46
> 0.1805E-03 - C 1 YY, SHELL 9, AO 21
> 0.6473E-04 - C 2 S, SHELL 16, AO 41
> 0.6473E-04 - C 1 S, SHELL 7, AO 16
> 0.2845E-04 - C 1 Y, SHELL 5, AO 8
> 0.2845E-04 - C 2 Y, SHELL 14, AO 33
> 0.8058E-05 - C 2 S, SHELL 12, AO 28
> 0.8058E-05 - C 1 S, SHELL 3, AO 3

> YOU MAY CONSIDER DROPPING ONE OR MORE AOS, STARTING FROM THE END OF THIS LIST.
>

Sat Oct 29 '11 3:11pm

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