I know analytic gradients are available for the CCSD, and the coupled-cluster package in Q-CHEM can calculate properties of target EOM states including permanent dipoles, angular momentum projections, static polarizabilities. So I want to know if I can get analytical polarizability from CCSD? I have tried to use the key word
$rem
JOBTYPE POLARIZABILITY
METHOD CCSD
BASIS aug-cc-pVDZ
MEM_TOTAL 120000
RESPONSE_POLAR 0
$end
but I find the output polarizability is actually the analytical polarizability from HF method. So can you give me an example of the input file if Q-chem can give analytical polarizability of CCSD?
See Section 7.10.20.8 of the manual. Examples are in Section 7.10.21.
https://manual.q-chem.com/latest/sec_EOMGRAD.html
I have tried to get the analytical polarizability using two methods. However, the results are different and neither is the same as the numerical results. So I am puzzled to use which method. Here are my input,
$rem
METHOD CCSD
BASIS aug-cc-pVDZ
MEM_TOTAL 200000
CC_REF_PROP 1
CC_POL 2
CC_DIIS_SIZE 15
CC_FULLRESPONSE 1
SYM_IGNORE TRUE
no_reorient true
$end
$rem
METHOD CCSD
BASIS aug-cc-pVDZ
MEM_TOTAL 200000
CC_REF_PROP 1
CC_POL 3
CC_DIIS_SIZE 15
CC_FULLRESPONSE 0
SYM_IGNORE TRUE
no_reorient true
$end
$rem
JOBTYPE POLARIZABILITY
METHOD CCSD
BASIS aug-cc-pVDZ
MEM_TOTAL 100000
RESPONSE_POLAR -1
FDIFF_STEPSIZE 10
SYM_IGNORE TRUE
no_reorient true
$end
the results are,
Polarizability Tensor ALPHA_IJ, I,J=X,Y,Z (a.u.):
------------------------------------------------------------------------------
44.82016642 -0.00040250 -0.00022886
-0.00040209 46.87450347 0.00056227
-0.00022878 0.00055402 33.88883125
------------------------------------------------------------------------------
Isotropic polarizability: 1/3 * (a_xx + a_yy + a_zz)
Isotropic polarizability in a.u. = 41.86116705
Anisotropic polarizability: SQRT(0.5*((a_xx-a_yy)^2 + (a_yy-a_zz)^2 + (a_zz-a_xx)^2))
Anisotropic polarizability in a.u. = 12.09012143
Polarizability Tensor ALPHA_IJ, I,J=X,Y,Z (a.u.):
------------------------------------------------------------------------------
-45.25278662 0.00049956 0.00022950
0.00049956 -47.70229233 -0.00063772
0.00022950 -0.00063772 -34.39252191
------------------------------------------------------------------------------
Isotropic polarizability: 1/3 * (a_xx + a_yy + a_zz)
Isotropic polarizability in a.u. = -42.44920029
Anisotropic polarizability: SQRT(0.5*((a_xx-a_yy)^2 + (a_yy-a_zz)^2 + (a_zz-a_xx)^2))
Anisotropic polarizability in a.u. = 12.26978843
and
Polarizability tensor [a.u.]
43.9396279 -0.0007206 -0.0002346
-0.0003291 45.8813873 0.0006981
-0.0002276 0.0009505 33.3528175
Principal components [a.u.]
33.3528175 43.9396276 45.8813876
Isotropic polarizability [a.u.]
41.0579442
Anisotropic polarizability [a.u.]
11.6793846
I know the two analytical polarizability results should be different as the incomplete basis, but I want to ask if I can trust the numerical resut?