Hyperpolarizability of HF


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Forum Vet
5:14:15 AM PDT - Sat, Mar 21st 2020
I first used B3LYP 6-311G++(2d,2p) by GAMESS to optimize HF, and then used NWCHEM7.0.0, GAMESS and Dalton2016.2 to calculate the hyperpolarizability of HF.

The NWCHEM input is

echo

start
memory stack 5500 mb heap 1500 mb global 7000 mb
geometry units angstroms print xyz
  symmetry c2v

  H 0       0        -0.04648

  F 0       0         0.87623
end

basis spherical
* library d-aug-cc-pVDZ
end

scf
 singlet

 rhf

 thresh 1.0e-8
end

tce
 scf

 ccsd

 maxiter 1000

 thresh 1.0e-9

 io ga

 2eorb

 2emet 13

 tilesize 28

 attilesize 40
end

set tce:lineresp T
set tce:leftresp T
set tce:respaxis T T T
set tce:afreq 0.0 0.0656
set tce:bfreq 0.0 0.0656

task tce energy
NWCHEM gives
CCSD Lambda Response polarizability / au 
Frequency  =       0.0000000 / au

Wavelength =        Infinity / nm
beta(Z,Z,Z) = 9.739286463 / au
...
CCSD Lambda Response polarizability / au 
Frequency  =      -0.0656000 / au

Wavelength =    -694.5633079 / nm
...
CCSD Quadratic Response
Static Hyperpolarizability       Why still called static?

-----------------------------------------------
beta(Z,Z,Z) = 8.461760589 / au
The original NWCHEM QA test using the following geometry

symmetry c2v
 H 0       0        0

 F 0       0        1.7328795 in terms of a.u.

gives

CCSD Quadratic Response
Static Hyperpolarizability

-----------------------------------------------

...

beta(Z,Z,Z) =        8.630759039 / au



   1 H                    1.0000     0.00000000     0.00000000    -1.55959155

   2 F                    9.0000     0.00000000     0.00000000     0.17328795


Dalton2016.2 using the same basis set and c2v symmetry gives
 ZDIPLEN  (unrel.) -0.0000   ZDIPLEN  (unrel.)  0.0000   ZDIPLEN  (unrel.)  0.0000      8.8915460    

                  -0.1312                      0.0656                      0.0656      9.7304868

GAMESS HF gives using basis set accdz and c2v symmetry
 Beta tensor [in au]( -0.131200;  0.065600,  0.065600)

                        x                y                z

  ...

  zz.        -0.000000        -0.000000       -10.171063

Reference Frequency-dependent hyperpolarizability of hydrogen fluoride gives
static beta(z,z,z)=-8.058
SHG beta(z,z,z)=-9.430 at Re=1.7328 a.u.

Very Best Regards!

Forum Vet
6:22:42 PM PDT - Sat, Mar 21st 2020
I use the specific GAMESS input making software waMacMolPlt to redraw the molecule, then use mp2 and 6-311G++(2d,2p) to find the following equilibrium geometry of HF having c2v geometry

F            9.0   0.0000000000   0.0000000000   0.1048050057

H           1.0   0.0000000000   0.0000000000  -0.8135350057

With GAMESS
...
Beta tensor [in au]( -0.000000; 0.000000, 0.000000)
              x                y                z

  zx.         0.704144        -0.000000        -0.000000

  zz.        -0.000000        -0.000000         9.926728
Beta tensor [in au]( -0.131200; 0.065600, 0.065600)
              x                y                z

  xz.         0.848328        -0.000000        -0.000000

  zx.         0.679234        -0.000000        -0.000000

  zz.        -0.000000        -0.000000        10.603235

The above reference gives (calculated)
SHG beta(zzz)=-9.430 beta(zxx)=-1.107 beta(xzx)=-1.276
static beta(zzz)=-8.722,-8.750 beta(zxx)=-1.045,-1.102
one indexed data there:static beta(zzz)=-9.838, beta(zxx)=-0.802
SCF:beta(zzz)=-8.808, beta(zxx)=-0.434

DALTO2016.2 gives 
                 +---------------------------------------------------------------------------------------+
! FINAL CCSD RESULTS FOR THE FIRST HYPERPOLARIZABILITIES !
+---------------------------------------------------------------------------------------+


A operator B operator C operator property


ZDIPLEN (unrel.) -0.0000 ZDIPLEN (unrel.) 0.0000 ZDIPLEN (unrel.) 0.0000 -8.6941344
-0.1312 0.0656 0.0656 -9.5090740








NWCHEM7.0.0 gives
CCSD Quadratic Response

Static Hyperpolarizability

-----------------------------------------------

beta(Z,X,X) =       -0.770738651 / au

beta(Z,Z,Z) =       -9.518810663 / au

CCSD Lambda Response polarizability / au 
Frequency  =      -0.0656000 / au

Wavelength =    -694.5633079 / nm



CCSD Quadratic Response

Static Hyperpolarizability

-----------------------------------------------



beta(X,Z,X) =       -0.581141625 / au

beta(Z,X,X) =       -0.581141625 / au

beta(Z,Z,Z) =       -8.275124709 / au

Reference Ab initio variational calculation of dynamic polarizabilities and hyperpolarizabilities I. Polarizability and quadratic hyperpolarizability of water, carbon monoxide and hydrogen fluoride gives the transformed experimental beta parallel of -5.45 at 694 nm, i.e., from reference Measurements of second- and third-order nonlinear polarizabilities for HF and HCI .

Dalton2016.2 HF gives, using d-aug-cc-pv-dz,

B-freq = 0.065600 C-freq = 0.065600 beta(Z;Z,Z) = -8.06145767
B-freq = 0.065600 C-freq = 0.065600 beta(Z;X,X) = 0.11285876
B-freq = 0.065600 C-freq = 0.065600 beta(X;Z,X) = -0.00022904
beta parellel=-1/5(3*8.06146-2*0.112859+4*0.00022904)=-4.79

GAMESS gives
beta parellel=-1/5(3*10.603235+2*0.679234+4*0.848328)=-7.31

NWCHEM7.0.0 gives
beta parallel-1/5(3*8.275+2*0.5811+4*0.5811)=-5.66

Beta parallel is calculatd baseed on Prof. Jorgensen's article Frequency dependent hyperpolarizability of hydrogen fluoride.
I am trying to repeat this for HF and calculate this organic molecules in solutions.


Very Best Regards!

Forum Vet
1:08:15 AM PDT - Sun, Mar 22nd 2020
CCSDT level calculation of this failed
...
CCSDT Linear Response polarizability / au 

Frequency  =       0.0656000 / au



                    



Frequency =       0.0000000 / au



CCSDT-YR (Static) iterations

---------------------------------------------

Iter          Residuum            Cpu    Wall

---------------------------------------------

key =                    90

                   1                    0

                   2                   10

                   3                   19

tce_hash: key not found                   0

------------------------------------------------------------------------

------------------------------------------------------------------------

 current input line : 

    0: 

------------------------------------------------------------------------

------------------------------------------------------------------------

This error has not yet been assigned to a category

------------------------------------------------------------------------

For more information see the NWChem manual at https://github.com/nwchemgit/nwchem/wiki




For further details see manual section: No section for this category

MPI_ABORT was invoked on rank 2 in communicator MPI COMMUNICATOR 3 DUP FROM 0
with errorcode -1.

NOTE: invoking MPI_ABORT causes Open MPI to kill all MPI processes.
You may or may not see output from other processes, depending on
exactly when Open MPI kills them.


The ccsd(t) level calculation only gives ccsd hyperpolarizability and ccsd(t) energy, etc.


I have put the log files on Github.

Forum Vet
2:22:52 AM PDT - Sun, Mar 29th 2020
I have run the recently implemented ducc and the hyperpolarizability calculation sequentially using 5 threads, all at ccsd level, and it works. I have put the log file on Github.

Although these cannot be used together now, I just wish to show this two can work sequentially.

Forum Vet
2:23:59 AM PDT - Sun, Mar 29th 2020
I have run the recently implemented ducc and the hyperpolarizability calculation sequentially using 5 threads, all at ccsd level, and it works. I have put the log file on Github.

Although these cannot be used together now, I just wish to show this two can work sequentially.

Very Best Regards!

Forum Vet
6:16:06 AM PDT - Sun, Mar 29th 2020
Measurements and Calculations of the Hyperpolarkabilities of Atoms and Small Molecules in the Gas Phase gives experimental beta=-11.0+-1.0 a.u. at 694.3 nm.

Table XIII. in this Chemical Reviews article gives beta (parallel) of -7.3 a.u. using ab initio.

Forum Vet
4:31:26 AM PDT - Sun, Apr 5th 2020
According to Table VIII in reference Molecular vibrational and rotational motion in static and dynamic fields, axial beta(vibrational) calculated can be 10.041,10.99 and 10.51, and beta(averaged over the vibrational gound state) calculated can be -10.505 and -8.47. It is stated in this reference there is a radical change in beta(zzz) when vibration is taken into consideration. GAMESS can calculate hyper-raman spectra. It is also said the discrepency betweem the calculated and the theoretical one is caused by the measured is for HF dimer.

I use 6-311G++(2d,2p) and mp2 with GAMESS to optimize initially linear HF dimer, get an nonlinear, planar equilibrium geometry, but its beta(zzz)es become zero or nearly zero. Whether is it correct?

From the dimer optimized structure, 276.76 pm is the distance between the two Fs, 92 pm is the length of each of the F-H bond, and 185.71 pm is the intermolecular hydrogen bond length. These agree with those in reference Benchmark calculations with correlated molecular wave functions. VII. Binding energy and structure of the HF dimer, where the dimer has no intermolecular hydrogen bond.

Very Best Regards!

Forum Vet
9:02:16 PM PDT - Sun, Apr 5th 2020
The aug-cc-pvdz CCSD calculation of beta(ZZZ) of HF using DALTON2016.2 and NWCHEM7.0.0 can give around -11.795a.u., and around -13.501a.u., respectively. NWCHEM 7.0.0 can give chi(parallel) around -4.53*10^-32 esu, close to the experimental value -4.70*10^-32 esu., but with d-aug-cc-pvdz, CCSD in NWCHEM7.0.0 only gives that of around-2.88*10^-32 esu.


No obvious changes caused by the employment of aug-cc-pvdz instead of d-aug-cc-pvdz using Dalton2016.2 and accd instead of accdc using GAMESS.

The optimization of an HF dimer with 6-311G++(2d,2p) and mp2 using GAMESS can give five additional hyper-Raman peaks and all around zero beta(zzz)es.

With HF Dalton2016.2 gives chi(parallel) around -3.58*10^-32 esu. , and GAMESS gives that around -3.68*10^-32 esu.

I have used Monte Carlo search with mini basis set first, then used b3lyp and 6-31G+(d) to optimize all-trans retinal, which is not easy to be optimized, and used HF to do Hessian analysis, obtaning its Thz spectra.

Very Best Regards!

Forum Vet
7:32:57 PM PDT - Wed, Apr 8th 2020
Reference Surface-Enhanced Hyper-Raman Spectra of Adenine, Guanine,Cytosine, Thymine, and Uracil gives experimental spectra of uracils.

Forum Vet
7:46:08 PM PDT - Wed, Apr 8th 2020
Hyper-Raman of gaseous Uracil has been calculated using GAMESS.

Forum Vet
7:43:58 PM PDT - Fri, Apr 10th 2020
According to the reference, the measured Hyper-Raman spectral are for Uracil anion because based on the previous SERS and DFT researches, it is deprotonated by the interactions with silver suraface, even at neutral pH. Since solvation and ROHF have not implemented in this kind of caculation, it cannot be guranteed that the calculation is good.

Forum Vet
5:41:10 AM PDT - Sat, Apr 11th 2020
In the reference, the anion forms of adenine, guanine and cytosin have not been mentioned, they can be tried for the Hyper-Raman calculation, but there may be some problems not considered, especially in the case of cytosine.

Forum Vet
7:06:29 PM PDT - Sat, Apr 11th 2020
I have chosen the following input with NWCHEM7.0.0 for uracil
...
basis spherical
 * library 6-31G**
end

dft
xc B3LYP
convergence energy 1d-8 nolevelshifting
direct
end

hessian
thresh 1d-8
profile
end

property
response 1 0.0856
damping 0.007
end

task dft raman


Very Best Regards!

Forum Vet
8:47:22 PM PDT - Mon, Apr 20th 2020
The calculation with the above input using NWCHEM7.0.0 on Ubuntu18.04 runs smoothly, but I do not know whether it can match experimental data.

I updated Mojave to Catlina, but encounted gethostname and other problem, and I went back to Mavericks, then upgraded to Majave, but still had gethostname problem. Since I forget how to edit hosts, I use Maveriks, which makes GAMESS binary up to 2019R2 running successfully, previsouly coupled cluster calculations becoming slower after GAMESS binary 2013 due to the upgrade of the operating system, and I will no longer compile NWCHEM and Dalton on Mac.

Very Best Regards!

Forum Vet
4:26:38 AM PDT - Sat, May 23rd 2020
I think we should be very careful when using the calculated BETA quantum chemically.

Very Best Regards!

Forum Vet
1:26:21 AM PDT - Sun, May 24th 2020
I have used the following in NWCHEM7.0.0 to calculate the dynamic Raman spectra of Cytosine, preoptimized by GAMESS using mp2 and 6-311++G(2d,2p),
...
basis spherical
 * library 6-31G*
end

dft
xc B3LYP
convergence energy 1d-8 nolevelshifting
direct
end

hessian
thresh 1d-8
profile
end

property
response 1 0.0856
damping 0.007
end

raman
 normal
end

task dft raman

According to the peak assignments in the reference,, the calculated frequencies of C2=O,bend NH2,str N3-C4-C5,C4-N8,one bend N1-H,C5-H,C6-H,one ring str C-N,C=O,ring breath, and two ring deles have deviances from the experimentally enhanced ones within 25 cm-1, where a few caluclated ones do not appear in the experimentAL TABLE and several experimental ones do not exhibit in the calculation. For these frequencies the strength can be predicted by the calculation except for one of the above.


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