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Large discrepancie exists for CS2 in gamma based on energy and dipole #64

Closed xiongyan21 closed 1 year ago

xiongyan21 commented 2 years ago

arge discrepancie exists for CS2 in gamma based on energy and dipole. The c2v mp2 finite differencing gives alpha an error around 3% when compared the experimental value indexed in Electric moments, polarizabilities and hyperpolarizabilities

But the calculated static gamma is below 10000 a.u. based on dipole and that based on energy is above 145000. TDHF caculated gamma at 800 nm is ~29% deviating from the experimental data in Hyperpolarizability dispersion measured for CS 2 vapor, and the indexed THG calcualted one there got an error of 38%. The calculated other methods got significant low gamma.

I am also not very sure how to transform (BOHR^7)/E^2 into another unit.

Very Best Regards!

xiongyan21 commented 2 years ago

SCF iteration of D2h of CS2 will give in mp2 finite field differencing ....

             RHF SCF CALCULATION
      --------------------------
 DENSITY MATRIX CONV=  1.00E-06

ITER EX DEM TOTAL ENERGY E CHANGE DENSITY CHANGE ORB. GRAD 1 0 0 -832.9723785930 -832.97237859306301.818677440 470.609284259 2 1 0-58506178.9814659134*2700.841870692** 3 2 0-90406102.3669507951*1266.253104492** 4 3 0-94795791.8172890544* 489.578274706** 5 0 0-95637776.6641262472* 155.308956929** 6 1 0-95814603.1904858053***** 1.919561914** 7 2 0-95814643.0699363500 -39.8794505447 0.9440606789462.042936917 8 3 0-95814646.6242172867 -3.5542809367 0.4083506614058.990441704 9 0 0-95814647.1726728529 -0.5484555662 0.1145846811652.737648798 10 1 0-95814647.2822403461 -0.1095674932 0.002200372 21.880480494 11 2 0-95814647.2822609842 -0.0000206381 0.000956564 9.628831564 12 3 0-95814647.2822634280 -0.0000024438 0.000400554 4.004277326 13 0 0-95814647.2822641134 -0.0000006855 0.000115648 1.639560061 ---------------START SECOND ORDER SCF--------------- 14 1 0-95814647.2822644860 -0.0000003725 0.000000381 0.003789460 15 2 0-95814647.2822644413 0.0000000447 0.000000118 0.001684032 16 3 0-95814647.2822639197 0.0000005215 0.000000004 0.000030266

Thus, it is wrong.

Very Best Regards!

xiongyan21 commented 2 years ago

Ref. 1 gives gamma calculated is ~10000 . For TDHF C2v and D2h gives no difference for THG gamma.

The calculated DC-EFISHG is around 1000 at 632.8 nm. and OKE is below 7000, significantly lower than experimental Kerr one indexed there for liquid CS2, but TDHF calculated static gamma is only below 6000.

Even with nosymmetry added, Dalton 2020 gives ... +---------------------------------------------------------+ ! FINAL CCSD RESULTS FOR THE SECOND-ORDER PROPERTIES ! +---------------------------------------------------------+

A operator B operator property

XDIPLEN (unrel.) -0.0000 XDIPLEN (unrel.) 0.0000 35.177661
-0.0570 0.0570 35.624404

XDIPLEN (unrel.) -0.0000 YDIPLEN (unrel.) 0.0000 0.64018931E-10 -0.0570 0.0570 0.65605591E-10

XDIPLEN (unrel.) -0.0000 ZDIPLEN (unrel.) 0.0000 0.15732227E-14 -0.0570 0.0570 0.17792739E-14

YDIPLEN (unrel.) -0.0000 XDIPLEN (unrel.) 0.0000 0.64018931E-10 -0.0570 0.0570 0.65605591E-10

YDIPLEN (unrel.) -0.0000 YDIPLEN (unrel.) 0.0000 35.177661
-0.0570 0.0570 35.624404

YDIPLEN (unrel.) -0.0000 ZDIPLEN (unrel.) 0.0000 0.48141745E-14 -0.0570 0.0570 0.54404940E-14

ZDIPLEN (unrel.) -0.0000 XDIPLEN (unrel.) 0.0000 0.15732227E-14 -0.0570 0.0570 0.17792739E-14

ZDIPLEN (unrel.) -0.0000 YDIPLEN (unrel.) 0.0000 0.48141745E-14 -0.0570 0.0570 0.54404940E-14

ZDIPLEN (unrel.) -0.0000 ZDIPLEN (unrel.) 0.0000 102.71795
-0.0570 0.0570 106.96707

...

Very Best Regards!