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ZEFF(n) array input for multiple atoms?

David Shobe
avidshobe@yahoo.com

On a closer look at Koseki et al., 1992 and Koseki et al, 1995, it appears that each nucleus does need its own Zeff.  But how do I input this into Firefly?  Will the following work?  5500 is the recommended Zeff for Sn, and 1 is the recommended Zeff for H.  The rest of the input file is the same as the input I asked about earlier.

$TRANST
   NUMVEC=1 NUMCI=1 NFZC=11 NOCC=13
   IROOTS(1)=2 NSTATE(1)=2 ZEFF(1)=5500.,1. CASTRF=.T.
$END

Or in other words, is ZEFF(n) to be interpreted as Zeff for the nth atom in the $DATA group?

Regards,
--David Shobe


On Thu Jun 15 '17 11:04pm, David Shobe wrote
--------------------------------------------
>Dear all--

>Given Alex's correction to my spin-orbit coupling calculation on Sn atom, I attempted to do a similar calculation on SnH.  I got a normal termination of Firefly, but are the results correct?  I'm particularly concerned about the Zeff parameter, which was determined for atomic tin only.  Maybe it doesn't matter much with a hydride, but if we have two or more heavy atoms as in TeBr, what Zeff should I use?

>Regards, and thanks for your help past and future,
>--David Shobe

>Here is my input file:
> $CONTRL SCFTYP=NONE CITYP=GUGA RUNTYP=SPINORBT MULT=2 ECP=READ $END
> $SYSTEM TIMLIM=60 MEMORY=1000000 $END
> $TRANST
>    NUMVEC=1 NUMCI=1 NFZC=11 NOCC=13
>    IROOTS(1)=2 NSTATE(1)=2 ZEFF(1)=5500. CASTRF=.T.
> $END
> $CIDRT1 GROUP=C1 FORS=.T. NFZC=11 NALP=1 NVAL=1 $END
> $DATA
>Tin hydride diatomic, spin-orbit using ROHF/cc-pVTZ-pp orbitals
>Cnv 4

>Sn  50.  0.0000000000   0.0000000000  -0.0384906767
>S   9
>  1   3672.4000000              0.0001170        
>  2    558.1430000              0.0006870        
>  3    114.0890000              0.0021300        
>  4     31.4006000             -0.0376690        
>  5     19.6318000              0.1591490        
>  6      6.7720500             -0.6517540        
>  7      1.8335100              0.8376920        
>  8      0.8777150              0.4884260        
>  9      0.0517570              0.0018720        
>S   9
>  1   3672.4000000              0.0000430        
>  2    558.1430000              0.0003070        
>  3    114.0890000              0.0004960        
>  4     31.4006000             -0.0091050        
>  5     19.6318000              0.0498980        
>  6      6.7720500             -0.2498540        
>  7      1.8335100              0.4440970        
>  8      0.8777150              0.3520250        
>  9      0.0517570             -0.1655790        
>S   1
>  1      0.2373960              1.0000000        
>S   1
>  1      0.1120680              1.0000000        
>S   1
>  1      0.0638000              1.0000000        
>P   9
>  1    216.9700000              0.0002260        
>  2     20.9102000              0.0229170        
>  3      8.7961100             -0.1971460        
>  4      2.5673700              0.4679170        
>  5      1.3145100              0.4960430        
>  6      0.6535910              0.1766100        
>  7      0.2721500              0.0128500        
>  8      0.1107360              0.0001190        
>  9      0.0440340              0.0001730        
>P   9
>  1    216.9700000             -0.0000810        
>  2     20.9102000             -0.0054570        
>  3      8.7961100              0.0530050        
>  4      2.5673700             -0.1546650        
>  5      1.3145100             -0.1589400        
>  6      0.6535910             -0.0497030        
>  7      0.2721500              0.3271270        
>  8      0.1107360              0.5670890        
>  9      0.0440340              0.2642970        
>P   1
>  1      0.3451000              1.0000000        
>P   1
>  1      0.0568000              1.0000000        
>D   7
>  1    130.2430000              0.0003190        
>  2     36.7762000              0.0026780        
>  3     14.6321000             -0.0101090        
>  4      4.6969500              0.1197680        
>  5      2.5307800              0.3226000        
>  6      1.3017400              0.3842380        
>  7      0.6465750              0.2653580        
>D   1
>  1      0.3023160              1.0000000        
>D   1
>  1      0.1160000              1.0000000        
>F   1
>  1      0.2822000              1.0000000        

>H  1. 0.0000000000   0.0000000000   1.7484906767  
>S   3
>  1     33.8700000              0.0060680        
>  2      5.0950000              0.0453080        
>  3      1.1590000              0.2028220        
>S   1
>  1      0.3258000              1.0000000        
>S   1
>  1      0.1027000              1.0000000        
>P   1
>  1      1.4070000              1.0000000        
>P   1
>  1      0.3880000              1.0000000        
>D   1
>  1      1.0570000              1.0000000        

> $END
> $ECP
>  SN-ECP GEN     28     4
>  1      ----- g-ul potential     -----
>      0.0000000        2      1.0000000        
>  2      ----- s-ul potential     -----
>    279.9886820        2     17.4204140        
>     62.3778100        2      7.6311550        
>  4      ----- p-ul potential     -----
>     66.1625230        2     16.1310240        
>    132.1743960        2     15.6280770        
>     16.3394170        2      7.3256080        
>     32.4889590        2      6.9425190        
>  4      ----- d-ul potential     -----
>     36.3874410        2     15.5149760        
>     54.5078410        2     15.1881600        
>      8.6968230        2      5.4560240        
>     12.8402080        2      5.3631050        
>  2      ----- f-ul potential     -----
>    -12.5763330        2     12.2823480        
>    -16.5959440        2     12.2721500    
>  H-ECP NONE    
> $END
>! orbital vectors taken from SnH_ro.pun.txt
> $VEC1
> 1  1 9.84452971E-01 3.36711135E-03 3.00872298E-02-2.68775182E-02-8.52980961E-03
> 1  2 0.00000000E+00 0.00000000E+00 6.10206305E-03 0.00000000E+00 0.00000000E+00
> 1  3 3.54931425E-03 0.00000000E+00 0.00000000E+00-3.52310185E-04 0.00000000E+00
> 1  4 0.00000000E+00-1.85886780E-03 2.25252947E-03 2.25252947E-03 7.54683837E-04
> 1  5 0.00000000E+00 0.00000000E+00 0.00000000E+00 3.48311503E-03 3.48311503E-03
> 1  6 3.02216051E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00 6.46051627E-03
> 1  7 6.46051627E-03 6.45564241E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 1  8 0.00000000E+00 0.00000000E+00-1.67715585E-03 0.00000000E+00-4.57681635E-04
> 1  9 0.00000000E+00-4.57681635E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 1 10 9.06057120E-05 5.01464864E-04 7.67544687E-05 0.00000000E+00 0.00000000E+00
> 1 11-3.96691163E-05 0.00000000E+00 0.00000000E+00-3.64284458E-04-1.30370495E-05
> 1 12-1.30370495E-05 1.13634958E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 2  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 2  2 0.00000000E+00 1.00030180E+00 0.00000000E+00 0.00000000E+00 2.69962585E-03
> 2  3 0.00000000E+00 0.00000000E+00 2.87829532E-04 0.00000000E+00 0.00000000E+00
> 2  4-1.50265259E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 2  5 0.00000000E+00 0.00000000E+00 3.29120753E-03 0.00000000E+00 0.00000000E+00
> 2  6 0.00000000E+00 0.00000000E+00 0.00000000E+00-8.26221408E-06 0.00000000E+00
> 2  7 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-2.00672918E-04
> 2  8 0.00000000E+00-9.22004130E-04 0.00000000E+00-4.12332778E-04 0.00000000E+00
> 2  9 0.00000000E+00 0.00000000E+00 0.00000000E+00-9.27483346E-04 0.00000000E+00
> 2 10 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 3.87305066E-05
> 2 11 0.00000000E+00 0.00000000E+00 2.59600604E-04 0.00000000E+00 0.00000000E+00
> 2 12 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-9.71844304E-05
> 3  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 3  2 1.00030180E+00 0.00000000E+00 0.00000000E+00 2.69962585E-03 0.00000000E+00
> 3  3 0.00000000E+00 2.87829532E-04 0.00000000E+00 0.00000000E+00-1.50265259E-03
> 3  4 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 3  5 0.00000000E+00 3.29120753E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 3  6 0.00000000E+00 0.00000000E+00-8.26221408E-06 0.00000000E+00 0.00000000E+00
> 3  7 0.00000000E+00 0.00000000E+00 0.00000000E+00-2.00672918E-04 0.00000000E+00
> 3  8-9.22004130E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 3  9-4.12332778E-04 0.00000000E+00-9.27483346E-04 0.00000000E+00 0.00000000E+00
> 3 10 0.00000000E+00 0.00000000E+00 0.00000000E+00 3.87305066E-05 0.00000000E+00
> 3 11 0.00000000E+00 2.59600604E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 3 12 0.00000000E+00 0.00000000E+00 0.00000000E+00-9.71844304E-05 0.00000000E+00
> 4  1 5.89075779E-03 3.05252346E-03-4.70626979E-04-4.30908274E-03 3.60852142E-05
> 4  2 0.00000000E+00 0.00000000E+00-9.98905998E-01 0.00000000E+00 0.00000000E+00
> 4  3 7.83490846E-03 0.00000000E+00 0.00000000E+00 2.12837865E-04 0.00000000E+00
> 4  4 0.00000000E+00-3.68660650E-03 1.33968967E-03 1.33968967E-03-5.81770162E-03
> 4  5 0.00000000E+00 0.00000000E+00 0.00000000E+00 1.00424328E-03 1.00424328E-03
> 4  6 3.35635198E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00 9.55357828E-04
> 4  7 9.55357828E-04 1.50972231E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 4  8 0.00000000E+00 0.00000000E+00-8.95704749E-04 0.00000000E+00-1.40962843E-03
> 4  9 0.00000000E+00-1.40962843E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 4 10-5.61611318E-04-1.94242345E-03-1.59640124E-04 0.00000000E+00 0.00000000E+00
> 4 11 3.40657526E-04 0.00000000E+00 0.00000000E+00 8.92355599E-04 1.14724769E-04
> 4 12 1.14724769E-04-2.26583297E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5  2 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5  3 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5  4 0.00000000E+00 0.00000000E+00 8.26011296E-01-8.26011296E-01 0.00000000E+00
> 5  5 0.00000000E+00 0.00000000E+00 0.00000000E+00 7.84492053E-02-7.84492053E-02
> 5  6 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 5.38730638E-03
> 5  7-5.38730638E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5  8 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 1.41950566E-03
> 5  9 0.00000000E+00-1.41950566E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5 10 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 5 11 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 5.25279586E-06
> 5 12-5.25279586E-06 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  2 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  3 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  4 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  5 9.53795688E-01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  6 0.00000000E+00 9.05853396E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  7 0.00000000E+00 0.00000000E+00 6.22072555E-03 0.00000000E+00 0.00000000E+00
> 6  8 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6  9 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 1.63910390E-03
> 6 10 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6 11 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 6 12 0.00000000E+00 0.00000000E+00 6.06539914E-06 0.00000000E+00 0.00000000E+00
> 7  1-1.48497576E-03 1.89263569E-03-8.34129806E-03 6.37520480E-03 4.94718279E-03
> 7  2 0.00000000E+00 0.00000000E+00-5.24369097E-03 0.00000000E+00 0.00000000E+00
> 7  3-1.15894678E-03 0.00000000E+00 0.00000000E+00-1.00588245E-03 0.00000000E+00
> 7  4 0.00000000E+00 1.09677971E-03-4.75190543E-01-4.75190543E-01 9.49117935E-01
> 7  5 0.00000000E+00 0.00000000E+00 0.00000000E+00-4.25397195E-02-4.25397195E-02
> 7  6 9.51830836E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00-4.92367953E-03
> 7  7-4.92367953E-03 1.00731012E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 7  8 0.00000000E+00 0.00000000E+00 5.37590648E-03 0.00000000E+00-2.37967542E-03
> 7  9 0.00000000E+00-2.37967542E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 7 10 1.36827567E-02 1.27065351E-02 5.66911699E-05 0.00000000E+00 0.00000000E+00
> 7 11-2.28310825E-03 0.00000000E+00 0.00000000E+00-1.17628875E-03-8.75372660E-05
> 7 12-8.75372660E-05 1.03070015E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 8  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 8  2 2.67687299E-03 0.00000000E+00 0.00000000E+00-7.84962026E-03 0.00000000E+00
> 8  3 0.00000000E+00-1.24534147E-03 0.00000000E+00 0.00000000E+00 4.37327179E-03
> 8  4 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 8  5 0.00000000E+00-9.53745005E-01 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 8  6 0.00000000E+00 0.00000000E+00-8.99017163E-02 0.00000000E+00 0.00000000E+00
> 8  7 0.00000000E+00 0.00000000E+00 0.00000000E+00-7.75432572E-03 0.00000000E+00
> 8  8 4.60565033E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 8  9 2.05970928E-03 0.00000000E+00-1.30883823E-03 0.00000000E+00 0.00000000E+00
> 8 10 0.00000000E+00 0.00000000E+00 0.00000000E+00-8.12047314E-04 0.00000000E+00
> 8 11 0.00000000E+00-6.40510465E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 8 12 0.00000000E+00 0.00000000E+00 0.00000000E+00 2.92532649E-04 0.00000000E+00
> 9  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 9  2 0.00000000E+00 2.67687299E-03 0.00000000E+00 0.00000000E+00-7.84962026E-03
> 9  3 0.00000000E+00 0.00000000E+00-1.24534147E-03 0.00000000E+00 0.00000000E+00
> 9  4 4.37327179E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
> 9  5 0.00000000E+00 0.00000000E+00-9.53745005E-01 0.00000000E+00 0.00000000E+00
> 9  6 0.00000000E+00 0.00000000E+00 0.00000000E+00-8.99017163E-02 0.00000000E+00
> 9  7 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-7.75432572E-03
> 9  8 0.00000000E+00 4.60565033E-03 0.00000000E+00 2.05970928E-03 0.00000000E+00
> 9  9 0.00000000E+00 0.00000000E+00 0.00000000E+00-1.30883823E-03 0.00000000E+00
> 9 10 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-8.12047314E-04
> 9 11 0.00000000E+00 0.00000000E+00-6.40510465E-04 0.00000000E+00 0.00000000E+00
> 9 12 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2.92532649E-04
>10  1 1.26735308E-02 4.78008755E-01-4.15939566E-01-3.96212961E-01 1.14720562E-01
>10  2 0.00000000E+00 0.00000000E+00 2.71253880E-02 0.00000000E+00 0.00000000E+00
>10  3-2.15120967E-01 0.00000000E+00 0.00000000E+00-1.16801175E-02 0.00000000E+00
>10  4 0.00000000E+00 8.00646580E-02-4.13651363E-02-4.13651363E-02 7.62729761E-02
>10  5 0.00000000E+00 0.00000000E+00 0.00000000E+00 1.92657534E-03 1.92657534E-03
>10  6-2.29110011E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00-1.06730425E-02
>10  7-1.06730425E-02-3.62967133E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00
>10  8 0.00000000E+00 0.00000000E+00-6.76627338E-03 0.00000000E+00 1.09692169E-02
>10  9 0.00000000E+00 1.09692169E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00
>10 10-1.22355271E-01-2.26505401E-01-1.40122598E-01 0.00000000E+00 0.00000000E+00
>10 11 5.52770154E-03 0.00000000E+00 0.00000000E+00 2.29092270E-02 1.95941975E-03
>10 12 1.95941975E-03-2.28911727E-03 0.00000000E+00 0.00000000E+00 0.00000000E+00
>11  1 3.41936739E-03-3.72836530E-01 3.01543921E-01 3.38866950E-01 1.18180005E-01
>11  2 0.00000000E+00 0.00000000E+00 2.22673613E-02 0.00000000E+00 0.00000000E+00
>11  3-6.26962399E-01 0.00000000E+00 0.00000000E+00-9.46426450E-03 0.00000000E+00
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>60  9 0.00000000E+00-9.93212967E-04 0.00000000E+00 0.00000000E+00 0.00000000E+00
>60 10-8.62687713E-03 2.87868147E-02 2.11445601E-03 0.00000000E+00 0.00000000E+00
>60 11-5.91333404E-03 0.00000000E+00 0.00000000E+00-1.57830820E-02-7.72570082E-03
>60 12-7.72570082E-03 1.29163394E-02 0.00000000E+00 0.00000000E+00 0.00000000E+00
> $END
>

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