The following three assignments are necessary in order to run a CAP-AIMD simulation:
JOBTYPE = AIMD in $rem,
COMPLEX_CCMAN = TRUE in $rem (see Section 7.10.9), and
CS_HF = 1 in $complex_ccman (see Section 7.10.9).
For now, CAP-AIMD simulations are possible only with the cuboid CAP type, so setting CAP_TYPE = 1 is also necessary in the $complex_ccman section (see Section 7.10.9).
With CAP-AIMD simulations, one gets two additional files in the AIMD directory (§9.9.2):
CAP_EComponents: Records for each step the total complex energy, the CAP-corrected total complex energy, and the real and imaginary parts of the CAP contribution to the total complex energy – all in atomic units (a.u.).
CAP_PositionAndWidth: Records for each step the total complex energy (in a.u.) and the resonance width (in electron-Volt).
CAP_AIMD_SWITCH
CAP_AIMD_SWITCH
Sets CAP_ETA to zero during a CAP-AIMD simulation when the real part of the last alpha occupied orbital’s energy is negative
TYPE:
LOGICAL
DEFAULT:
TRUE
OPTIONS:
TRUE
Set CAP_ETA to zero when the real part of the last alpha occupied orbital’s becomes negative.
FALSE
Keep user’s CAP_ETA constant throughout simulation.
RECOMMENDATION:
Use default.
CS_STRICT
CS_STRICT
Determines Mulliken charges, multipole moments and complex orbital energies for CAP-HF calculations by reading, when applicable, complex density matrix or complex molecular orbital coefficient file
TYPE:
LOGICAL
DEFAULT:
FALSE
OPTIONS:
TRUE
determine Mulliken charges, multipole moments and complex orbital energies for CAP-HF calculations by reading – when applicable – the complex density matrix or complex molecular orbital coefficient file.
FALSE
Don’t read the complex density matrix or complex molecular orbital coefficient file when determining Mulliken charges, multipole moments and orbital energies for CAP-HF calculations.
RECOMMENDATION:
Set to ‘TRUE’ for CAP-HF calculations.
SKIP_OLD_SCFMAN
SKIP_OLD_SCFMAN
Skips only old SCF drivers
TYPE:
LOGICAL
DEFAULT:
FALSE
OPTIONS:
TRUE
Skip only old SCF drivers
FALSE
Do not skip old SCF drivers
RECOMMENDATION:
When performing CAP calculations on temporary anions, it may help setting this variable to FALSE.
CS_SCF_FINAL_PRINT
CS_SCF_FINAL_PRINT
Controls level of output from CAP-SCF procedure.
TYPE:
INTEGER
DEFAULT:
0
No extra print out.
OPTIONS:
1
Print direct breakdown of CAP-SCF energy.
2
Print breakdown of CAP-SCF energy based on the complex coefficient matrix.
Also required if the options below are requested.
3
Level 2 plus diagonal elements of complex orbital energy matrix, F. Triggered by Level 2.
4
Level 2 plus diagonal elements of complex kinetic energy matrix, T. Triggered by Level 2
5
Level 2 plus diagonal elements of complex electron-nuclear Coulomb potential energy matrix, V. Triggered by Level 2.
6
Level 2 plus diagonal elements of CAP matrix, W. Triggered by Level 2.
7
Level 2 plus diagonal elements of total complex one-electron energy matrix, . Triggered by Level 2.
8
Level 2 plus diagonal elements of total complex electronic energy matrix, . Triggered by Level 2.
9
Level 2 to 8. Triggered by Level 2.
RECOMMENDATION:
Level 1 is usually enough. Values for this $rem variable are transformed first into a set of distinct values;
thus, for example, “1111” is equivalent to “1” and “28224” is equivalent to “248”.
To request Levels 3–9, please remember to request Level 2 as well.
Example 9.9.45 CAP-HF single point job for N, with energy decomposition of the complex energy. Basis set is cc-PVTZ+3p.
$molecule
-1 2
N
N 1 1.098
$end
$rem
¯JOBTYPE¯¯SP
¯METHOD¯¯¯hf
¯BASIS¯¯¯general
¯GEN_SCFMAN¯¯TRUE
¯SKIP_OLD_SCFMAN¯true¯! skip old scfman drivers
¯SCF_CONVERGENCE¯8
¯SCF_GUESS¯¯CORE
¯COMPLEX_CCMAN¯¯TRUE
¯UNRESTRICTED¯¯TRUE
¯CS_STRICT¯¯TRUE¯! Determine orbital energies and props. using the complex density matrix/complex MO coefficients
¯CS_SCF_FINAL_PRINT¯1111¯! Print summary of energy decomposition
$end
$complex_ccman
¯CS_HF ¯¯¯1
¯CAP_TYPE ¯¯1
¯CAP_ETA ¯¯420
¯CAP_X ¯¯¯3535
¯CAP_Y ¯¯¯3535
¯CAP_Z ¯¯¯8102
$end
$basis
N 0
S 7 1.00
11420. 0.00052898
1712. 0.00409115
389.3 0.02101161
110.0 0.08163835
35.57 0.23564992
12.54 0.43792615
4.644 0.35006007
S 7 1.00
11420. 0.00000185
1712. 0.00000699
110.0 -0.00073647
35.57 -0.00718168
12.54 -0.04679022
4.644 -0.12512392
0.5118 0.78627029
S 1 1.00
1.293 1.000000
S 1 1.00
0.1787 1.000000
P 3 1.00
26.63 0.014670
5.948 0.091764
1.742 0.298683
P 1 1.00
0.5550 1.000000
P 1 1.00
0.1725 1.000000
D 1 1.00
1.654 1.000000
D 1 1.00
0.469 1.000000
F 1 1.00
1.093 1.000000
¯P 1 1.00
¯¯0.08625 1.000000
¯P 1 1.00
¯¯0.043125 1.000000
¯P 1 1.00
¯¯0.0215625 1.000000
****
$end
Example 9.9.46 CAP-AIMD simulation for N. Basis set is cc-PVTZ+3p.
$molecule
-1 2
N
N 1 1.098
$end
$rem
JOBTYPE¯¯AIMD
METHOD¯¯¯HF
BASIS¯¯¯GENERAL
GEN_SCFMAN¯¯TRUE
SKIP_OLD_SCFMAN¯TRUE¯¯! Skip old scfman drivers
SCF_CONVERGENCE¯8
MAX_SCF_CYCLES¯¯200
SCF_GUESS¯¯CORE
COMPLEX_CCMAN¯¯TRUE¯¯! Activate Complex CCMAN. Necessary for CAP calculations.
UNRESTRICTED¯¯TRUE
TIME_STEP¯¯10
AIMD_STEPS¯¯200
FOCK_EXTRAP_ORDER 0
FOCK_EXTRAP_POINTS 0
AIMD_MOMENTS¯¯1
AIMD_TEMP¯¯300
AIMD_INIT_VELOC¯THERMAL
CAP_AIMD_SWITCH¯TRUE¯¯! Set CAP_ETA=0 when extra electron is bound
CS_STRICT¯¯TRUE¯¯! Determine orbital energies and props. using the complex density. matrix/complex MO coefficients
INTEGRAL_SYMMETRY FALSE
POINT_GROUP_SYMMETRY FALSE
$end
$complex_ccman
¯CS_HF ¯¯¯1¯¯! Do complex HF
¯CAP_TYPE ¯¯1¯¯! CAP type is cuboid.
¯CAP_ETA ¯¯420
¯CAP_X ¯¯¯3535
¯CAP_Y ¯¯¯3535
¯CAP_Z ¯¯¯8102
$end
$basis
N 0
S 7 1.00
11420. 0.00052898
1712. 0.00409115
389.3 0.02101161
110.0 0.08163835
35.57 0.23564992
12.54 0.43792615
4.644 0.35006007
S 7 1.00
11420. 0.00000185
1712. 0.00000699
110.0 -0.00073647
35.57 -0.00718168
12.54 -0.04679022
4.644 -0.12512392
0.5118 0.78627029
S 1 1.00
1.293 1.000000
S 1 1.00
0.1787 1.000000
P 3 1.00
26.63 0.014670
5.948 0.091764
1.742 0.298683
P 1 1.00
0.5550 1.000000
P 1 1.00
0.1725 1.000000
D 1 1.00
1.654 1.000000
D 1 1.00
0.469 1.000000
F 1 1.00
1.093 1.000000
¯P 1 1.00
¯¯0.08625 1.000000
¯P 1 1.00
¯¯0.043125 1.000000
¯P 1 1.00
¯¯0.0215625 1.000000
****
$end
Example 9.9.47 CAP-AIMD simulation for CH. Basis set is cc-PVTZ+3p(C).
A CAP single point calculation is first done. The CAP-SCF solution is then read as the initial guess for the CAP-AIMD part. This procedure is useful, for example, when one wants to use the MOM_START option (§4.5.13) to preserve orbital occupation in the course of the simulation.
$molecule
-1 2
C 0.0000 0.0000 0.0000
H 0.0000 0.0000 1.0742
H 0.9596 0.0000 -0.4829
C -1.1191 0.0000 -0.6897
H -2.0787 0.0000 -0.2068
H -1.1191 0.0000 -1.7639
$end
$rem
METHOD¯¯¯HF
BASIS¯¯¯GENERAL
GEN_SCFMAN¯¯TRUE
SKIP_OLD_SCFMAN¯TRUE¯! skip old scfman drivers
SCF_CONVERGENCE¯8
SCF_GUESS¯¯CORE
COMPLEX_CCMAN¯¯TRUE
UNRESTRICTED¯¯TRUE
CS_STRICT¯¯TRUE¯! Determine orbital energies and props. using the complex density matrix/complex MO coefficients
CS_SCF_FINAL_PRINT¯1111¯! Print summary of energy decomposition
INTEGRAL_SYMMETRY ¯FALSE
POINT_GROUP_SYMMETRY¯FALSE
$end
$complex_ccman
CS_HF ¯¯¯1
CAP_TYPE ¯¯1
CAP_ETA ¯¯230
CAP_X ¯¯¯4360
CAP_Y ¯¯¯2680
CAP_Z ¯¯¯4360
$end
$basis
H¯0
cc-pvtz
****
C 0
S 8 1.00
8236.0000000 0.0005310
1235.0000000 0.0041080
280.8000000 0.0210870
79.2700000 0.0818530
25.5900000 0.2348170
8.9970000 0.4344010
3.3190000 0.3461290
0.3643000 -0.0089830
S 8 1.00
8236.0000000 -0.0001130
1235.0000000 -0.0008780
280.8000000 -0.0045400
79.2700000 -0.0181330
25.5900000 -0.0557600
8.9970000 -0.1268950
3.3190000 -0.1703520
0.3643000 0.5986840
S 1 1.00
11.8760000 1.0000000
S 1 1.00
4.2920000 1.0000000
S 1 1.00
0.9059000 1.0000000
S 1 1.00
0.1285000 1.0000000
P 3 1.00
18.7100000 0.0140310
4.1330000 0.0868660
1.2000000 0.2902160
P 1 1.00
33.1900000 1.0000000
P 1 1.00
8.7780000 1.0000000
P 1 1.00
0.3827000 1.0000000
P 1 1.00
0.1209000 1.0000000
D 1 1.00
14.8390000 1.0000000
D 1 1.00
1.0970000 1.0000000
D 1 1.00
0.3180000 1.0000000
F 1 1.00
0.7610000 1.0000000
P¯1¯¯1.00
¯¯0.06045¯1.00
P¯1¯¯1.00
¯¯0.030225¯1.00
P¯1¯¯1.00
¯¯0.0151125¯1.00
****
$end
@@@
$molecule
READ
$end
$velocity
3.6095e-05 4.1623e-06 2.3754e-05
-9.7386e-04 -1.4552e-05 -1.2310e-03
-2.8737e-04 1.2165e-04 2.9068e-04
3.3619e-05 -1.3939e-04 1.0849e-04
6.4312e-04 2.0187e-04 -4.2066e-04
-2.1196e-04 1.3012e-03 -2.1364e-04
$end
$rem
¯JOBTYPE¯¯AIMD
¯METHOD¯¯¯HF
¯BASIS¯¯¯GENERAL
¯GEN_SCFMAN¯¯TRUE
¯SKIP_OLD_SCFMAN¯TRUE
¯SCF_CONVERGENCE¯8
¯MAX_SCF_CYCLES¯¯3000
integral_symmetry FALSE
point_group_symmetry False
¯SCF_GUESS¯¯READ
¯COMPLEX_CCMAN¯¯TRUE
¯UNRESTRICTED¯¯TRUE
¯MOM_START¯¯1
¯MOM_METHOD¯¯MOM
¯TIME_STEP¯¯2
¯AIMD_STEPS¯¯200
¯FOCK_EXTRAP_ORDER 0
¯FOCK_EXTRAP_POINTS 0
¯AIMD_MOMENTS¯¯1
¯AIMD_PRINT¯¯2¯! Print Mulliken charges and dipole moments at each step
¯CS_STRICT¯¯TRUE
$end
$complex_ccman
¯CS_HF ¯¯¯1
¯CAP_TYPE ¯¯1
¯CAP_ETA ¯¯230
¯CAP_X ¯¯¯4360
¯CAP_Y ¯¯¯2680
¯CAP_Z ¯¯¯4360
$end
$basis
H¯0
cc-pvtz
****
C 0
S 8 1.00
8236.0000000 0.0005310
1235.0000000 0.0041080
280.8000000 0.0210870
79.2700000 0.0818530
25.5900000 0.2348170
8.9970000 0.4344010
3.3190000 0.3461290
0.3643000 -0.0089830
S 8 1.00
8236.0000000 -0.0001130
1235.0000000 -0.0008780
280.8000000 -0.0045400
79.2700000 -0.0181330
25.5900000 -0.0557600
8.9970000 -0.1268950
3.3190000 -0.1703520
0.3643000 0.5986840
S 1 1.00
11.8760000 1.0000000
S 1 1.00
4.2920000 1.0000000
S 1 1.00
0.9059000 1.0000000
S 1 1.00
0.1285000 1.0000000
P 3 1.00
18.7100000 0.0140310
4.1330000 0.0868660
1.2000000 0.2902160
P 1 1.00
33.1900000 1.0000000
P 1 1.00
8.7780000 1.0000000
P 1 1.00
0.3827000 1.0000000
P 1 1.00
0.1209000 1.0000000
D 1 1.00
14.8390000 1.0000000
D 1 1.00
1.0970000 1.0000000
D 1 1.00
0.3180000 1.0000000
F 1 1.00
0.7610000 1.0000000
P¯1¯¯1.00
¯¯0.06045¯1.00
P¯1¯¯1.00
¯¯0.030225¯1.00
P¯1¯¯1.00
¯¯0.0151125¯1.00
****
$end