CC_STATE_TO_OPT
CC_STATE_TO_OPT
Specifies which state to optimize (or from which state compute EOM-EOM inter-state
properties).
TYPE:
INTEGER ARRAY
DEFAULT:
None
OPTIONS:
[,]
optimize the th state of the th irrep.
RECOMMENDATION:
None
Note: The state number should be smaller or equal to the number of excited states calculated in the corresponding irrep.
Note: If analytic gradients are not available, the finite difference calculations will be performed and the symmetry will be turned off. In this case, CC_STATE_TO_OPT should be specified assuming C symmetry, i.e., as [1,N] where N is the number of state to optimize (the states are numbered from 1).
CC_EOM_PROP
CC_EOM_PROP
Whether or not the non-relaxed (expectation value) one-particle EOM-CCSD
target state properties will be calculated. Available properties currently include
permanent dipole moment, angular momentum projections, the second moments
(, , and )
of the electron density along with
.
This option is incompatible with
JOBTYPE = FORCE, OPT, or FREQ.
TYPE:
LOGICAL
DEFAULT:
FALSE (no one-particle properties will be calculated)
OPTIONS:
FALSE, TRUE
RECOMMENDATION:
Additional equations (EOM-CCSD equations for the left eigenvectors) need to be
solved for properties, approximately doubling the cost of calculation for each
irrep.
The cost of the one-particle properties calculation itself is low. The
one-particle density of an EOM-CCSD target state can be analyzed with NBO or
libwfa packages by specifying the state with CC_STATE_TO_OPT and
requesting NBO = TRUE and CC_EOM_PROP = TRUE.
CC_TRANS_PROP
CC_TRANS_PROP
Whether or not the transition dipole moment (in atomic units) and oscillator
strength and rotatory strength (in atomic units)
for the EOM-CCSD target states will be calculated. By default, the
transition dipole moment, angular momentum matrix elements,
and rotatory strengths
are calculated between the CCSD reference and the
EOM-CCSD target states. In order to calculate transition dipole moment, angular momentum matrix elements,
and rotatory strengths between a set of EOM-CCSD states and another EOM-CCSD state, the
CC_STATE_TO_OPT
must be specified for this state.
TYPE:
INTEGER
DEFAULT:
0 (no transition properties will be calculated)
OPTIONS:
1 (calculate transition properties between all computed EOM state and the reference state)
2 (calculate transition properties between all pairs of EOM states)
RECOMMENDATION:
Additional equations (for the left EOM-CCSD eigenvectors plus lambda CCSD
equations in case of transition properties between the CCSD reference and
EOM-CCSD target states are requested) need to be solved for transition
properties, approximately doubling the computational cost. The cost of the
transition properties calculation itself is low.
Note: When the $trans_prop section is present in the input, it overrides the setting of the CC_TRANS_PROP $rem variable. However, for $trans_prop to work, CC_TRANS_PROP does need to be set.
CC_EOM_ECD
CC_EOM_ECD
Whether or not the ECD transition moments will be calculated. By default, the
transition moments are calculated between the CCSD reference and the
EOM-CCSD target states. In order to calculate transition moments between
a set of EOM-CCSD states and another EOM-CCSD state, the
CC_STATE_TO_OPT must be specified for this state.
TYPE:
LOGICAL
DEFAULT:
FALSE (do not compute ECD transition moments)
OPTIONS:
TRUE
Compute ECD transition moments.
RECOMMENDATION:
Activate for chiral molecules only.
CC_EOM_2PA
CC_EOM_2PA
Whether or not the transition moments and cross-sections for two-photon
absorption will be calculated. By default, the
transition moments are calculated between the CCSD reference and the
EOM-CCSD target states. In order to calculate transition moments between
a set of EOM-CCSD states and another EOM-CCSD state, the
CC_STATE_TO_OPT must be specified for this state.
If 2PA NTO analysis is requested, the CC_EOM_2PA value is redundant
as long as CC_EOM_2PA .
TYPE:
INTEGER
DEFAULT:
0 (do not compute 2PA transition moments)
OPTIONS:
1
Compute 2PA using the fastest algorithm (use -intermediates for
canonical
and -intermediates for RI/CD response calculations).
2
Use -intermediates for 2PA response equation calculations.
3
Use -intermediates for 2PA response equation calculations.
RECOMMENDATION:
Additional response equations (6 for each target state) will be solved,
which increases the cost of calculations. The cost of 2PA
moments is about 10 times that of energy calculation.
Use the default algorithm.
Setting CC_EOM_2PA turns on CC_TRANS_PROP.
CC_EOM_2PA_XCONV
CC_EOM_2PA_XCONV
Convergence criterion for the response vectors (norm of the difference)
of the DIIS solver for damped response equations in 2PA and RIXS calculations.
TYPE:
INTEGER
DEFAULT:
5 Corresponding to
OPTIONS:
Corresponding to convergence criterion.
RECOMMENDATION:
Use the default in double precision. May reduce in single precision.
DAMPED_DALTON_SOLVER
DAMPED_DALTON_SOLVER
Boolean for using the new Davidson-like solver (Dalton) for damped
(CCSD polarizabilities and hyperpolarizabilities and EOM-CCSD 2PA and RIXS cross sections) response equations.
TYPE:
LOGICAL
DEFAULT:
TRUE (Use the new Dalton solver)
OPTIONS:
FALSE
If the old DIIS solver is desired for the above properties.
RECOMMENDATION:
Use the new solver for faster convergence relative to DIIS.
DALTON_XCONV
DALTON_XCONV
Convergence criterion for the residuals (square norm) of the Dalton solver for response equations.
TYPE:
INTEGER
DEFAULT:
6 Corresponding to
OPTIONS:
Corresponding to convergence criterion.
RECOMMENDATION:
Use the default in double precision. May reduce to 5 in single precision.
DALTON_MAXITER
DALTON_MAXITER
Maximum number of iteration allowed for the Dalton solver for response equations.
TYPE:
INTEGER
DEFAULT:
100
OPTIONS:
User-defined number of iterations.
RECOMMENDATION:
Default is usually sufficient
DALTON_MAXSPACE
DALTON_MAXSPACE
Specifies maximum number of vectors in the subspace for the Dalton solver for response equations.
TYPE:
INTEGER
DEFAULT:
200
OPTIONS:
Up to vectors per root before the subspace is reset.
RECOMMENDATION:
Larger values increase disk storage but accelerate and stabilize convergence.
DALTON_PRECOND_START
DALTON_PRECOND_START
Specifies the iteration number in the Dalton procedure for response equations from which the preconditioner is applied to the residuals.
TYPE:
INTEGER
DEFAULT:
1
OPTIONS:
User-defined iteration number.
RECOMMENDATION:
Use default.
CALC_SOC
CALC_SOC
Whether or not the spin-orbit couplings between CC/EOM/ADC/CIS/TDDFT electronic states
will be calculated. In the CC/EOM-CC suite, by default the couplings are calculated between
the CCSD reference and the EOM-CCSD target states. In order to calculate
couplings between EOM states, CC_STATE_TO_OPT must specify
the initial EOM state. If NTO analysis is requested, analysis of spinless transition density matrices
will be performed and the spin-orbit integrals over NTO pairs will be printed.
TYPE:
INTEGER/LOGICAL
DEFAULT:
FALSE (no spin-orbit couplings will be calculated)
OPTIONS:
0/FALSE
(no spin-orbit couplings will be calculated)
1/TRUE
Activates SOC calculation. EOM-CC/EOM-MP2 only: spin-orbit couplings will be computed with the new code with L+/L- averaging
2
EOM-CC/EOM-MP2 only: spin-orbit couplings will be computed with the new code without L+/L- averaging
3
EOM-CC/EOM-MP2 only: spin-orbit couplings will be computed with the legacy code
4
One-electron spin-orbit couplings will be computed with effective nuclear charges (with L+/L- averaging
for EOM-CC/MP2)
RECOMMENDATION:
CCMAN2 supports several variants of SOC calculation for EOM-CC/EOM-MP2 methods.
One-electron and mean-field two-electron SOCs will be computed by default.
To enable full two-electron SOCs, two-particle EOM properties must be
turned on (see CC_EOM_PROP_TE).
CALC_NAC
CALC_NAC
Whether or not nonadiabatic couplings
will be calculated for the EOM-CC, CIS, and TDDFT wave functions.
TYPE:
INTEGER
DEFAULT:
0 (do not compute NAC)
OPTIONS:
1
NYI for EOM-CC
2
Compute NACs using Szalay’s approach (this what needs to be specified for EOM-CC).
RECOMMENDATION:
Additional response equations will be solved and gradients for all EOM states and
for summed states will be computed,
which increases the cost of calculations.
Request only when needed and do not ask for too many EOM states.
CC_POL
CC_POL
Specifies the approach for calculating the polarizability of the CCSD wave function.
TYPE:
INTEGER
DEFAULT:
0
(CCSD polarizability will not be calculated)
OPTIONS:
1
(analytic-derivative or response-theory mixed symmetric-asymmetric approach)
2
(analytic-derivative or response-theory asymmetric approach)
3
(expectation-value approach with right response intermediates)
4
(expectation-value approach with left response intermediates)
13
(damped-response expectation-value approach with right response intermediates)
14
(damped-response expectation-value approach with left response intermediates)
15
(damped-response expectation-value approach with first-order response density matrices)
RECOMMENDATION:
CCSD polarizabilities are expensive since they require solving
three/six (for static) or six/twelve (for dynamic)
additional response equations. Do no request this property unless you need it.
EOM_POL
EOM_POL
Specifies the approach for calculating the polarizability of the EOM-CCSD wave function.
TYPE:
INTEGER
DEFAULT:
0
(EOM-CCSD polarizability will not be calculated)
OPTIONS:
1
(analytic-derivative or response-theory mixed symmetric-asymmetric approach)
2
(analytic-derivative or response-theory asymmetric approach)
3
(expectation-value approach with right response intermediates)
4
(expectation-value approach with left response intermediates)
RECOMMENDATION:
EOM-CCSD polarizabilities are expensive since they require solving
three/nine (for static) or six/eighteen (for dynamic)
additional response equations. Do no request this property unless you need it.
CC_1HPOL
CC_1HPOL
Specifies the approach for calculating the first hyperpolarizability of the CCSD wave function.
TYPE:
INTEGER
DEFAULT:
0
(CCSD first hyperpolarizability will not be calculated)
OPTIONS:
1
(damped-response expectation-value approach with only first-order response wave functions)
3
(damped-response expectation-value approach with second-order response density matrices for wave-function and natural orbital analyses)
RECOMMENDATION:
CCSD first hyperpolarizabilities are expensive since they require solving a huge number of first- and second-order response equations.
Do no request this property unless you need it.
CC_EOM_PROP_TE
CC_EOM_PROP_TE
Request for calculation of non-relaxed two-particle EOM-CC properties. The
two-particle properties currently include . The one-particle
properties also will be calculated, since the additional cost of the
one-particle properties calculation is inferior compared to the cost of
. The variable CC_EOM_PROP must be also set to
TRUE. Alternatively, CC_CALC_SSQ can be used to
request calculation.
TYPE:
LOGICAL
DEFAULT:
FALSE
(no two-particle properties will be calculated)
OPTIONS:
FALSE, TRUE
RECOMMENDATION:
The two-particle properties are computationally expensive since
they require calculation and use of the two-particle density matrix (the cost
is approximately the same as the cost of an analytic gradient calculation). Do
not request the two-particle properties unless you really need them.
CC_FULLRESPONSE
CC_FULLRESPONSE
Fully relaxed properties (with or without orbital relaxation terms) will be computed.
The variable CC_EOM_PROP must be also set to TRUE.
TYPE:
INTEGER
DEFAULT:
0
(no amplitude and orbital response will be calculated)
OPTIONS:
1
(both amplitude and orbital response will be calculated)
2
(only amplitude response will be calculated)
RECOMMENDATION:
Not available for non-UHF/RHF references. Only available for EOM/CI methods for which analytic
gradients are available.
CC_SYMMETRY
CC_SYMMETRY
Controls the use of symmetry in coupled-cluster calculations
TYPE:
LOGICAL
DEFAULT:
TRUE
OPTIONS:
TRUE
Use the point group symmetry of the molecule
FALSE
Do not use point group symmetry (all states will be of symmetry).
RECOMMENDATION:
It is automatically turned off for any finite difference calculations, e.g.
second derivatives.
STATE_ANALYSIS
STATE_ANALYSIS
Activates excited state analyses using libwfa.
TYPE:
LOGICAL
DEFAULT:
FALSE (no excited state analyses)
OPTIONS:
TRUE, FALSE
RECOMMENDATION:
Set to TRUE if excited state analysis is required, but also if plots
of densities or orbitals are needed. For details see
Section 10.2.11.
G_TENSOR
G_TENSOR
Activates g-tensor calculation.
TYPE:
LOGICAL
DEFAULT:
FALSE
OPTIONS:
FALSE (or 0)
Don’t calculate g-tensor
TRUE (or 1)
Calculate g-tensor.
RECOMMENDATION:
None.
Note: g-Tensor calculations are only available for CCSD.
Example 7.108 Geometry optimization for the excited open-shell singlet state, , of methylene followed by the calculations of the fully relaxed one-electron properties using EOM-EE-CCSD.
$molecule 0 1 C H 1 rCH H 1 rCH 2 aHCH rCH = 1.083 aHCH = 145. $end $rem JOBTYPE OPT METHOD EOM-CCSD BASIS cc-pVTZ SCF_GUESS CORE SCF_CONVERGENCE 9 EE_SINGLETS [0,0,0,1] EOM_NGUESS_SINGLES 2 CC_STATE_TO_OPT [4,1] EOM_DAVIDSON_CONVERGENCE 9 use tighter convergence for EOM amplitudes $end @@@ $molecule read $end $rem METHOD EOM-CCSD BASIS cc-pVTZ SCF_GUESS READ EE_SINGLETS [0,0,0,1] EOM_NGUESS_SINGLES 2 CC_EOM_PROP 1 calculate properties for EOM states CC_FULLRESPONSE 1 use fully relaxed properties $end
Example 7.109 Property and transition property calculation on the lowest singlet state of CH using EOM-SF-CCSD.
$molecule 0 3 C H 1 rch H 1 rch 2 ahch rch = 1.1167 ahch = 102.07 $end $rem METHOD eom-ccsd BASIS cc-pvtz SCF_GUESS core SCF_CONVERGENCE 9 SF_STATES [2,0,0,3] Get three 1^B2 and two 1^A1 SF states CC_EOM_PROP 1 CC_TRANS_PROP 1 CC_STATE_TO_OPT [4,1] First EOM state in the 4th irrep $end
Example 7.110 Calculation of EOM transition strength using length, momentum, and mixed gauges.
$comment
EOM-CC oscillator strength using three gauges
$end
$molecule
0 1
C 1.2509987 -0.0000000 0.0000000
C -1.2509987 0.0000000 -0.0000000
H 2.3262529 1.8903377 0.4190778
H 2.3262529 -1.8903377 -0.4190778
H -2.3262529 1.8903377 -0.4190778
H -2.3262529 -1.8903377 0.4190778
$end
$rem
method = ccsd
input_bohr = true
ee_singlets [0,0,2,2]
basis = 6-31g
cc_trans_prop = true
cc_ref_prop = 1
cc_eom_prop = 1
$end
$trans_prop
state_list
ref
ee_singlets 0 0
end_list
calc dipole linmom
$end
Example 7.111 Calculation of ECD using EOM-CCSD wavefunctions.
$comment
Calculation of ECD using EOM-CC wave-functions
$end
$molecule
0 1
C 1.2509987 -0.0000000 0.0000000
C -1.2509987 0.0000000 -0.0000000
H 2.3262529 1.8903377 0.4190778
H 2.3262529 -1.8903377 -0.4190778
H -2.3262529 1.8903377 -0.4190778
H -2.3262529 -1.8903377 0.4190778
$end
$rem
method = ccsd
input_bohr = true
ee_singlets [0,0,2,2]
basis = 6-31g
cc_trans_prop = true
cc_ref_prop = 1
cc_eom_prop = 1
cc_eom_ecd = 1 ! keyword to activate ECD
$end
@@@
$comment
Calculation of ECD using EOM-CC wave-functions
using trans_prop section
$end
$molecule
0 1
C 1.2509987 -0.0000000 0.0000000
C -1.2509987 0.0000000 -0.0000000
H 2.3262529 1.8903377 0.4190778
H 2.3262529 -1.8903377 -0.4190778
H -2.3262529 1.8903377 -0.4190778
H -2.3262529 -1.8903377 0.4190778
$end
$rem
method = ccsd
input_bohr = true
ee_singlets [0,0,2,2]
basis = 6-31g
cc_trans_prop = true
cc_ref_prop = 1
cc_eom_prop = 1
$end
$trans_prop
state_list
ref
ee_singlets 0 0
end_list
calc ecd
$end
Example 7.7.112 Geometry optimization with tight convergence for the A excited state of CHCl, followed by calculation of non-relaxed and fully relaxed permanent dipole moment and .
$molecule 0 2 H C 1 CH CL 2 CCL 1 CCLH H 2 CH 3 CCLH 1 DIH CH = 1.096247 CCL = 2.158212 CCLH = 122.0 DIH = 180.0 $end $rem JOBTYPE OPT METHOD EOM-CCSD BASIS 6-31G* Basis Set SCF_GUESS SAD EOM_DAVIDSON_CONVERGENCE 9 EOM amplitude convergence CC_T_CONV 9 CCSD amplitudes convergence EE_STATES [0,0,0,1] CC_STATE_TO_OPT [4,1] EOM_NGUESS_SINGLES 2 GEOM_OPT_TOL_GRADIENT 2 GEOM_OPT_TOL_DISPLACEMENT 2 GEOM_OPT_TOL_ENERGY 2 $end @@@ $molecule read $end $rem METHOD EOM-CCSD BASIS 6-31G* Basis Set SCF_GUESS READ EE_STATES [0,0,0,1] EOM_NGUESS_SINGLES 2 CC_EOM_PROP 1 calculate one-electron properties CC_EOM_PROP_TE 1 and two-electron properties (S^2) $end @@@ $molecule read $end $rem METHOD EOM-CCSD BASIS 6-31G* Basis Set SCF_GUESS READ EE_STATES [0,0,0,1] EOM_NGUESS_SINGLES 2 CC_EOM_PROP 1 calculate one-electron properties CC_EOM_PROP_TE 1 and two-electron properties (S^2)CC_EXSTATES_PROP 1 CC_FULLRESPONSE 1 same as above, but do fully relaxed properties $end
Example 7.113 CCSD calculation on three and one state of formaldehyde. Transition properties will be calculated between the third state and all other EOM states.
$molecule 0 1 O C 1 1.4 H 2 1.0 1 120 H 2 1.0 1 120 3 180 $end $rem BASIS 6-31+G METHOD EOM-CCSD EE_STATES [0,3,0,1] CC_STATE_TO_OPT [2,3] CC_TRANS_PROP true $end
Example 7.114 EOM-IP-CCSD geometry optimization of X state of .
$molecule 0 1 H 0.774767 0.000000 0.458565 O 0.000000 0.000000 -0.114641 H -0.774767 0.000000 0.458565 $end $rem JOBTYPE opt METHOD eom-ccsd BASIS 6-311G IP_STATES [0,0,0,1] CC_STATE_TO_OPT [4,1] $end
Example 7.7.115 CAP-EOM-EA-CCSD geometry optimization of the anionic resonance state of formaldehyde. The applied basis is aug-cc-pVDZ augmented by 3s3p diffuse functions on heavy atoms.
$molecule
0 1
C 0.0000000000 0.0000000000 0.5721328608
O 0.0000000000 0.0000000000 -0.7102635035
H 0.9478180646 0.0000000000 1.1819748108
H -0.9478180646 0.0000000000 1.1819748108
$end
$rem
JOBTYPE opt
METHOD eom-ccsd
BASIS gen
N_FROZEN_CORE 0
SCF_CONVERGENCE 9
CC_CONVERGENCE 9
EOM_DAVIDSON_CONVERGENCE 9
EA_STATES [0,0,0,2]
CC_STATE_TO_OPT [4,1]
XC_GRID 000250000974
COMPLEX_CCMAN 1
$end
$complex_ccman
CS_HF 1
CAP_TYPE 1
CAP_ETA 60
CAP_X 3850
CAP_Y 2950
CAP_Z 6100
$end
$basis
H 0
S 3 1.00
13.0100000 0.196850000E-01
1.96200000 0.137977000
0.444600000 0.478148000
S 1 1.00
0.122000000 1.00000000
P 1 1.00
0.727000000 1.00000000
S 1 1.00
0.297400000E-01 1.00000000
P 1 1.00
0.141000000 1.00000000
****
C 0
S 8 1.00
6665.00000 0.692000000E-03
1000.00000 0.532900000E-02
228.000000 0.270770000E-01
64.7100000 0.101718000
21.0600000 0.274740000
7.49500000 0.448564000
2.79700000 0.285074000
0.521500000 0.152040000E-01
S 8 1.00
6665.00000 -0.146000000E-03
1000.00000 -0.115400000E-02
228.000000 -0.572500000E-02
64.7100000 -0.233120000E-01
21.0600000 -0.639550000E-01
7.49500000 -0.149981000
2.79700000 -0.127262000
0.521500000 0.544529000
S 1 1.00
0.159600000 1.00000000
P 3 1.00
9.43900000 0.381090000E-01
2.00200000 0.209480000
0.545600000 0.508557000
P 1 1.00
0.151700000 1.00000000
D 1 1.00
0.550000000 1.00000000
S 1 1.00
0.469000000E-01 1.00000000
P 1 1.00
0.404100000E-01 1.00000000
D 1 1.00
0.151000000 1.00000000
S 1 1.00
0.234500000E-01 1.00000000
S 1 1.00
0.117250000E-01 1.00000000
S 1 1.00
0.058625000E-01 1.00000000
P 1 1.00
0.202050000E-01 1.00000000
P 1 1.00
0.101025000E-01 1.00000000
P 1 1.00
0.050512500E-01 1.00000000
****
O 0
S 8 1.00
11720.0000 0.710000000E-03
1759.00000 0.547000000E-02
400.800000 0.278370000E-01
113.700000 0.104800000
37.0300000 0.283062000
13.2700000 0.448719000
5.02500000 0.270952000
1.01300000 0.154580000E-01
S 8 1.00
11720.0000 -0.160000000E-03
1759.00000 -0.126300000E-02
400.800000 -0.626700000E-02
113.700000 -0.257160000E-01
37.0300000 -0.709240000E-01
13.2700000 -0.165411000
5.02500000 -0.116955000
1.01300000 0.557368000
S 1 1.00
0.302300000 1.00000000
P 3 1.00
17.7000000 0.430180000E-01
3.85400000 0.228913000
1.04600000 0.508728000
P 1 1.00
0.275300000 1.00000000
D 1 1.00
1.18500000 1.00000000
S 1 1.00
0.789600000E-01 1.00000000
P 1 1.00
0.685600000E-01 1.00000000
D 1 1.00
0.332000000 1.00000000
S 1 1.00
0.394800000E-01 1.00000000
S 1 1.00
0.197400000E-01 1.00000000
S 1 1.00
0.098700000E-01 1.00000000
P 1 1.00
0.342800000E-01 1.00000000
P 1 1.00
0.171400000E-01 1.00000000
P 1 1.00
0.085700000E-01 1.00000000
****
$end
Example 7.116 Calculating resonant 2PA with degenerate photons.
$molecule 0 1 O H 1 0.959 H 1 0.959 2 104.654 $end $rem METHOD eom-ccsd BASIS aug-cc-pvtz EE_SINGLETS [1,0,0,0] 1A_1 state CC_TRANS_PROP 1 Compute transition properties CC_EOM_2PA 1 Calculate 2PA cross-sections using the fastest algorithm $end
Example 7.117 Non-degenerate, resonant 2PA scan over a range of frequency pairs.
$molecule 0 1 O H 1 0.959 H 1 0.959 2 104.654 $end $rem METHOD eom-ccsd BASIS aug-cc-pvdz EE_SINGLETS [2,0,0,0] !Two A_1 states CC_TRANS_PROP 1 !Calculate transition properties CC_EOM_2PA 1 !Calculate 2PA cross-sections using the fastest algorithm $end $2pa n_2pa_points 11 omega_1 500000 5000 $end
Example 7.118 Resonant 2PA with degenerate photons between two excited states.
$molecule 0 1 O H 1 0.959 H 1 0.959 2 104.654 $end $rem METHOD eom-ccsd BASIS aug-cc-pvtz EE_SINGLETS [2,0,0,0] Two A_1 states CC_STATE_TO_OPT [1,1] "Reference" state for transition properties is 1A_1 state CC_TRANS_PROP 1 Compute transition properties CC_EOM_2PA 1 Calculate 2PA cross-sections using the fastest algorithm $end
Example 7.119 Calculation of 1st hyperpolarizability for CCSD wave function for LiH using the framework of damped response theory and the expectation-value approach for a range of frequencies.
$comment Calculation of static and dynamical first hyperpolarizability for CCSD wave function for LiH with STO-3G basis set using the framework of damped response theory and the expectation-value approach. The property for the following set of photons is calculated: (omega_1, omega_2; omega_3) in cm-1 (0, 0; 0), (2500, 0; -2500), (5000, 0; -5000), (0, 3500; -3500), (0, 7000; -7000), (2500, 3500; -6000), (2500, 7000; -9500), (5000, 3500; -8500), (5000, 7000; -12000) $end $molecule 0 1 H Li 1 1.6 $end $rem METHOD ccsd BASIS sto-3g CC_REF_PROP 1 ! required for CCSD property calculation CC_1HPOL 1 ! computes first hyperpolarizability using first-order response wave functions only MEM_STATIC 400 CC_MEMORY 2000 THRESH 13 SCF_CONVERGENCE 10 CC_CONVERGENCE 9 $end $1hpol omega_1 0 2500000 3 0.01 ! scans the first photon frequency from 0 cm-1 to 5000 cm-1 in 3-1=2 steps of 2500, corresponding damping is 0.01 hartrees omega_2 0 3500000 3 0.01 ! scans the second photon frequency from 0 cm-1 to 7000 cm-1 in 3-1=2 steps of 3500, corresponding damping is 0.01 hartrees omega_3 0.01 ! damping for the third photon is 0.01 hartrees $end
Example 7.120 Mean-field spin-orbit calculation between two excited triplets in acetylene-O intermediate.
$molecule 0 1 C -0.0303943366 -0.3149506151 -0.0436827067 H -0.1031279784 -1.4353675705 -0.1647400816 O 1.0178175761 0.2350702146 0.2517598501 C -1.3252768442 0.1905302054 -0.4205132671 H -2.0767072171 0.1461814657 0.3842573052 $end $rem BASIS cc-pvdz METHOD eom-ccsd point_group_symmetry False SF_STATES [2] CC_STATE_TO_OPT [1,1] THRESH 14 CALC_SOC 1 CC_TRANS_PROP 1 $end
Example 7.121 Mean-field spin-orbit calculation between the reference singlet and excited triplet states for acetylene-O intermediate.
$molecule 0 1 C -0.0303943366 -0.3149506151 -0.0436827067 H -0.1031279784 -1.4353675705 -0.1647400816 O 1.0178175761 0.2350702146 0.2517598501 C -1.3252768442 0.1905302054 -0.4205132671 H -2.0767072171 0.1461814657 0.3842573052 $end $rem BASIS cc-pvdz METHOD eom-ccsd point_group_symmetry False EE_TRIPLETS [1] THRESH 14 CALC_SOC 1 CC_TRANS_PROP 1 $end
Example 7.122 Computation of spin-orbit couplings between closed-shell singlet and triplet state in NH using EOM-SF-CCSD.
$molecule 0 3 N H N 1.0450 $end $rem METHOD = eom-ccsd BASIS = 6-31g SF_STATES = [1,2,0,0] CC_TRANS_PROP = true CALC_SOC = 3 ! legacy code CC_STATE_TO_OPT = [1,1] $end
Example 7.123 Computation of spin-orbit couplings in neutral hextet (tpa)Fe complex (stripped ligands) by EOM-EA-MP2 method using pseudopotentials and effective nuclear charges.
$comment Spin-orbit coupling calculation with SBKJC ecp using default effective nuclear charges. Computes SOC in neutral hextet (tpa)Fe geometry (stripped ligands) by EOM-EA-MP2 method and high-spin reference. $end $molecule 0 6 N -0.0330663 -0.2576466 1.3744726 N 2.0052862 -0.4826730 -0.5758819 N -1.9801232 -0.6573608 -0.6407513 N -0.0634263 1.4157074 -0.9056826 Fe 0.0133915 -0.5560750 -0.6002859 H -0.0630940 -1.1802863 1.8620650 H -0.8780689 0.2958440 1.6401738 H 2.3459249 -0.6439674 -1.5498484 H 2.3506743 -1.2708551 0.0162081 H -2.2816187 -0.8324531 -1.6252623 H -2.3957415 0.2480261 -0.3283621 H 0.0565056 1.5985967 -1.9267087 H 0.7257691 1.8766147 -0.3993792 H 0.8165651 0.2643868 1.6852415 $end $rem METHOD = EOM-MP2 EOM_EA_BETA = [5] MAX_SCF_CYCLES = 300 SCF_ALGORITHM = gdm SCF_GUESS = autosad EOM_PRECONV_SINGLES = 1 CALC_SOC = 4 CC_TRANS_PROP = 2 BASIS = SBKJC [ use effective charges of ecps in soc calculation] ECP = fit-SBKJC $end
Example 7.124 Computation of spin-orbit coupling in ClO using all-electron basis set, user-provided effective nuclear charges, and EOM-IP wave-functions.
$comment Spin-orbit coupling calculation using all-electron basis set and user-provided effective nuclear charges by using EOM-IP wave-functions. $end $molecule -1 1 Cl -0.9937913 -0.6696391 -1.9087016 O 0.3415336 -0.1593825 -1.2619353 $end $rem jobtype = sp method = eom-ccsd basis = 6-31G print_general_basis = 1 scf_convergence = 12 cc_convergence = 10 eom_davidson_conv = 8 eom_ip_alpha = [0,0,1,1] cc_eom_prop = 1 cc_ref_prop = 1 cc_trans_prop = 1 cc_state_to_opt = [3,1] calc_soc = 4 $end $soc_eff_charges 8.0 6.0 17.0 11.0 $end
Example 7.125 Computation of nonadiabatic couplings between EOM-EE states within triplet (first job) and singlet (second job) manifolds.
$molecule +1 1 H 0.00000 0.00000 0.0 He 0.00000 0.00000 3.0 $end $rem JOBTYPE = FORCE METHOD = EOM-CCSD BASIS = cc-pVDZ INPUT_BOHR = true EE_TRIPLETS = [2] CC_EOM_PROP = true POINT_GROUP_SYMMETRY = false Do not reorient molecule and turn off YYYYYYYYYYYY CALC_NAC = 2 Invoke Szalay NAC EOM_DAVIDSON_CONVERGENCE = 9 tight davidson convergence SCF_CONVERGENCE = 9 Hartree-Fock convergence threshold 1e-9 CC_CONVERGENCE = 9 $end @@@ $molecule read $end $rem JOBTYPE = FORCE METHOD = EOM-CCSD BASIS = cc-pVDZ INPUT_BOHR = true EE_STATES = [2] singlets POINT_GROUP_SYMMETRY = false Do not reorient molecule and turn off YYYYYYYYYYYY CALC_NAC = 2 Invoke Szalay NAC EOM_DAVIDSON_CONVERGENCE = 9 tight davidson convergence SCF_CONVERGENCE = 9 Hartree-Fock convergence threshold 1e-9 CC_CONVERGENCE = 9 $end
Example 7.126 Calculation of the static dipole polarizability of the CCSD wave function of Helium.
$molecule 0 1 He $end $rem METHOD ccsd BASIS cc-pvdz CC_REF_PROP 1 CC_POL 2 CC_DIIS_SIZE 15 CC_FULLRESPONSE 1 $end
Example 7.127 Water molecule: Calculating photoionization cross-section and photoelectron angular distribution with averaging over molecular orientations.
$comment
Calculating photoionization cross-section and photoelectron angular distribution
with averaging over molecular orientations.
$end
$molecule
0 1
O 0.000000000000 0.000000000000 -0.004762594898
H 0.000000000000 0.801842648150 -0.560344690289
H 0.000000000000 -0.801842648150 -0.560344690289
$end
$rem
JOB_TYPE = SP
METHOD = EOM-CCSD
BASIS = 6-31G*
EOM_IP_ALPHA = [1,0,0,1]
CC_DO_DYSON = TRUE
CC_FREE_ELECTRON = 1
MEM_TOTAL = 4000
$end
$free_electron
N_ENERGY_POINTS 10
N_THETA 25
N_PHI 10
SPIN_DEG 2
ORB_DEG 1
DO_AVERAGE 1
KE_MIN 10
KE_MAX 1010
$end
Example 7.128 Water molecule: Calculating photoionization cross-section, asymmetry parameter and photoelectron angular distribution with a Z-polarized light.
$comment
Calculating photoionization cross-section, asymmetry parameter, and PAD
with a Z-polarized light.
$end
$molecule
0 1
O 0.000000000000 0.000000000000 -0.004762594898
H 0.000000000000 0.801842648150 -0.560344690289
H 0.000000000000 -0.801842648150 -0.560344690289
$end
$rem
JOB_TYPE = SP
METHOD = EOM-CCSD
BASIS = 3-21G
purecart = 1111
EOM_IP_ALPHA = [1,0,0,1]
CC_DO_DYSON = TRUE
CC_FREE_ELECTRON = 1
MEM_TOTAL = 4000
$end
$free_electron
N_ENERGY_POINTS 10
N_THETA 25
N_PHI 10
SPIN_DEG 2
ORB_DEG 1
POL_X 0
POL_Y 0
POL_Z 100
KE_MIN 10
KE_MAX 1010
$end
Example 7.129 Water molecule: Calculating photoionization cross-section and photoelectron angular distribution with averaging over molecular orientations.
$comment
Calculating photoionization cross-section and PAD
with averaging over molecular orientations.
$end
$molecule
0 1
O 0.000000000000 0.000000000000 -0.004762594898
H 0.000000000000 0.801842648150 -0.560344690289
H 0.000000000000 -0.801842648150 -0.560344690289
$end
$rem
JOB_TYPE = SP
METHOD = EOM-CCSD
BASIS = 6-31G*
EOM_IP_ALPHA = [1,0,0,1]
CC_DO_DYSON = TRUE
CC_FREE_ELECTRON = 1
MEM_TOTAL = 4000
$end
$free_electron
N_ENERGY_POINTS 10
N_THETA 25
N_PHI 10
SPIN_DEG 2
ORB_DEG 1
DO_AVERAGE 1
KE_MIN 10
KE_MAX 1010
$end
Example 7.130 Calculating photoionization cross-sections for the ionization of oxygen 1s (core) of water with Z-polarized light.
$comment
Calculating photoionization cross-sections for the ionization of oxygen 1s (core)
of water with Z-polarized light.
$end
$molecule
0 1
O 0.000000000000 0.000000000000 -0.004762594898
H 0.000000000000 0.801842648150 -0.560344690289
H 0.000000000000 -0.801842648150 -0.560344690289
$end
$rem
JOB_TYPE = SP
METHOD = EOM-CCSD
BASIS = 3-21G
purecart = 1111
CVS_IP_STATES = [1,0,0,0]
N_FROZEN_CORE = FC
CC_DO_DYSON = TRUE
CC_FREE_ELECTRON = 1
MEM_TOTAL = 4000
$end
$free_electron
N_ENERGY_POINTS 10
N_THETA 25
N_PHI 10
SPIN_DEG 2
ORB_DEG 1
POL_X 0
POL_Y 0
POL_Z 100
KE_MIN 10
KE_MAX 1010
$end
Example 7.131 Calculating photoionization cross-section, asymmetry parameter, and PAD with a circularly polarized light.
$comment
Calculating photoionization cross-section, asymmetry parameter, and
PAD with a circularly polarized light.
$end
$molecule
0 1
C -0.28956361 0.08176958 0.92701577
C 1.93885200 -1.15600766 -0.10800484
C -2.79852375 -0.19094696 -0.27656907
O 1.53613696 1.47730615 -0.46998636
H 1.71860882 -2.32670888 -1.80795335
H 3.52273536 -1.64526642 1.13875511
H -0.27744501 0.50560530 2.96417187
H -2.56905279 -0.59002862 -2.30639911
H -3.89960425 1.56511541 -0.07933409
H -3.88892566 -1.73605572 0.59599929
$end
$rem
JOB_TYPE = SP
METHOD = EOM-CCSD
BASIS = 3-21G
INPUT_BOHR = TRUE
EOM_IP_ALPHA = [2]
CC_DO_DYSON = TRUE
CC_FREE_ELECTRON = 1
MEM_TOTAL = 4000
$end
$free_electron
N_ENERGY_POINTS 10
N_THETA 15
N_PHI 10
SPIN_DEG 2
ORB_DEG 1
CIRC_POL 1
DO_AVERAGE 0
KE_MIN 10
KE_MAX 1010
$end