CISelect in RASSCF problem

Posted by Mariusz Radon on January 04, 2006 at 15:55:57:

I'm trying to select 2 roots in RASSCF module for future converging state average of them. The relevant fragment of input is

CIRoot
2 20 1
CISelect
1
798
1.0
1
390
1.0

so 2 of 20 roots computed in Davidson method are needed for orbital optimisation -- the ones which have maximum overlap with CSFs no 798 and 390.

The problem is that printed CI coefficients are inconsistent with the results of selection. Having done 10 RASSCF iterations, the biggest contribution from CSF 798 has the root number 3 while the root number 6 is dominated by the CSF 390. But CI coefficients shows that it is the root 1 (not 3!)that has the highest CSF798 contribution. The CSF390 contribution is the highest in root 6 (this time agreeing with the CISelect). Furthermore, the printed overlaps (0.415 and 0.572) are not consistent in any way with CI coefficients from expansion of roots number 1 and 6, which are 0.86725 and -0.90987. (The coefficient for CSF798 in root 3 is zero!)

The output (not converged, because these are just testing calculations for proper root selection -- I believe this is not the reason of problem) is as follows:

RASSCF iterations: Energy and convergence statistics
----------------------------------------------------

Iter CI SX CI RASSCF Energy max BLB max BLB max ROT Level Ln srch Step QN Time(min)
iter iter root energy change element value param shift minimum type update CPU
1 1 6 0 -2756.13728258 0.00E+00 107 264 1 -0.57E-02 0.21E+00 0.93 0.00 SX NO 24.34
No convergence in the CI section: MAXJT will be increased to
52
new roots selected: 2 15
overlap 0.414 0.478
2 50 26 0 -2756.06496758 0.72E-01 99 110 1 -0.19E-01 0.21E+00 0.94 0.00 LS NO 12.65
new roots selected: 2 17
overlap 0.415 0.673
3 12 27 0 -2756.05178221 0.13E-01 108 174 1 0.34E-01 0.20E+00 0.93 0.06 LS NO 12.44
new roots selected: 2 20
overlap 0.414 0.471
4 11 19 0 -2756.04241535 0.94E-02 59 108 1 0.34E-01 0.30E+00 0.93 -0.50 LS NO 12.42
new roots selected: 2 19
overlap 0.415 0.698
5 38 28 0 -2756.05300894 -0.11E-01 108 174 1 0.38E-01 0.44E+00 0.93 2.50 LS NO 12.62
new roots selected: 2 19
overlap 0.415 0.700
6 10 30 0 -2756.05265003 0.36E-03 108 174 1 0.38E-01 -0.45E-01 0.93 0.40 SX NO 12.42
No convergence in the CI section: MAXJT will be increased to
54
new roots selected: 3 10
overlap 0.415 0.545
7 52 10 0 -2756.07254002 -0.20E-01 107 166 1 -0.76E-02 0.48E-01 0.93 1.08 QN YES 12.54
new roots selected: 3 6
overlap 0.416 0.596
8 53 10 0 -2756.07900970 -0.65E-02 59 117 1 0.78E-02 0.61E-01 0.93 1.05 QN YES 12.59
new roots selected: 3 6
overlap 0.415 0.612
9 43 12 0 -2756.08131850 -0.23E-02 107 166 1 0.70E-02 -0.28E-01 0.93 1.10 QN YES 12.52
new roots selected: 3 6
overlap 0.415 0.588
10 19 10 0 -2756.08262033 -0.13E-02 107 166 1 0.71E-02 -0.18E-01 0.93 1.63 LS YES 12.34
No convergence after 10 iterations
new roots selected: 3 6
overlap 0.415 0.572
11 14 10 0 -2756.08311313 -0.49E-03 107 166 1 0.71E-02 -0.18E-01 0.93 1.63 LS YES 12.28

************************************************************************************************************************
Wave function printout:
occupation of active orbitals, and spin coupling of open shells (u,d: Spin up or down)
************************************************************************************************************************

printout of CI-coefficients larger than 0.05 for root 1
energy= -2756.163895
conf/sym 11111111 Coeff Weight
483 u2202200 -0.05394 0.00291
798 uu2d2200 -0.93126 0.86725
803 uu2d2020 0.09218 0.00850
806 uu2d0220 0.09002 0.00810
810 uu2ddudu 0.06934 0.00481
821 uu2duudd 0.13786 0.01900
824 uu2d2002 0.08112 0.00658
827 uu2d0202 0.09044 0.00818
1043 u0222200 0.09606 0.00923
1631 uu20220d 0.22328 0.04985

printout of CI-coefficients larger than 0.05 for root 2
energy= -2756.126110
conf/sym 11111111 Coeff Weight
390 uu22d200 -0.10287 0.01058
1008 uud22200 -0.91622 0.83947
1013 uud22020 0.09109 0.00830
1016 uud20220 0.08653 0.00749
1020 uud2dudu 0.07109 0.00505
1031 uud2uudd 0.13779 0.01899
1034 uud22002 0.08505 0.00723
1037 uud20202 0.09108 0.00829
1336 uudd220u 0.13708 0.01879
1775 uudu220d 0.24385 0.05946

printout of CI-coefficients larger than 0.05 for root 3
energy= -2756.094782
conf/sym 11111111 Coeff Weight
623 202u2200 0.25924 0.06721
658 ud2u2200 0.86144 0.74207
663 ud2u2020 -0.08526 0.00727
666 ud2u0220 -0.08326 0.00693
670 ud2ududu -0.07313 0.00535
681 ud2uuudd -0.12188 0.01486
684 ud2u2002 -0.07505 0.00563
687 ud2u0202 -0.08363 0.00699
693 022u2200 -0.25906 0.06711
1043 u0222200 -0.05666 0.00321
1176 2020220u -0.06156 0.00379
1196 ud20220u -0.20455 0.04184
1216 0220220u 0.06153 0.00379

printout of CI-coefficients larger than 0.05 for root 4
energy= -2756.094692
conf/sym 11111111 Coeff Weight
623 202u2200 0.61427 0.37733
628 202u2020 -0.06077 0.00369
631 202u0220 -0.05933 0.00352
635 202ududu -0.05214 0.00272
646 202uuudd -0.08691 0.00755
649 202u2002 -0.05356 0.00287
652 202u0202 -0.05963 0.00356
658 ud2u2200 -0.36648 0.13431
681 ud2uuudd 0.05185 0.00269
693 022u2200 -0.60393 0.36473
698 022u2020 0.05980 0.00358
701 022u0220 0.05841 0.00341
705 022ududu 0.05127 0.00263
716 022uuudd 0.08545 0.00730
719 022u2002 0.05258 0.00276
722 022u0202 0.05864 0.00344
1078 0u222200 0.05672 0.00322
1176 2020220u -0.14633 0.02141
1196 ud20220u 0.08704 0.00758
1216 0220220u 0.14295 0.02044

printout of CI-coefficients larger than 0.05 for root 5
energy= -2756.072865
conf/sym 11111111 Coeff Weight
389 uu222d00 0.92870 0.86248
397 uu220d20 0.09997 0.00999
407 uu22u0dd -0.11830 0.01399
411 uu220d02 0.07856 0.00617
800 uu2dd2u0 -0.06420 0.00412
807 uu2d2d0u -0.06689 0.00447
815 uu2d2u0d 0.07049 0.00497
1546 uu2ud2d0 0.11199 0.01254
1549 uu2u2d0d 0.22578 0.05098
1640 uu202d02 0.12243 0.01499

printout of CI-coefficients larger than 0.05 for root 6
energy= -2756.071444
conf/sym 11111111 Coeff Weight
390 uu22d200 -0.90987 0.82787
396 uu22d020 0.09761 0.00953
408 uu220udd 0.11726 0.01375
410 uu22d002 0.06725 0.00452
799 uu2d2du0 -0.06934 0.00481
808 uu2dd20u 0.06762 0.00457
816 uu2du20d -0.08121 0.00660
1008 uud22200 0.06097 0.00372
1336 uudd220u -0.05733 0.00329
1545 uu2u2dd0 0.13215 0.01746
1550 uu2ud20d -0.23719 0.05626
1641 uu20d202 -0.12293 0.01511
1775 uudu220d -0.11848 0.01404

Follow Ups:

Post a Followup

Name:
E-Mail:

Subject:

if B is 1s22s22p1, what is Li?

Passfield:

Comments:
: I'm trying to select 2 roots in RASSCF module for future converging state average of them. The relevant fragment of input is : CIRoot : 2 20 1 : CISelect : 1 : 798 : 1.0 : 1 : 390 : 1.0 : so 2 of 20 roots computed in Davidson method are needed for orbital optimisation -- the ones which have maximum overlap with CSFs no 798 and 390. : The problem is that printed CI coefficients are inconsistent with the results of selection. Having done 10 RASSCF iterations, the biggest contribution from CSF 798 has the root number 3 while the root number 6 is dominated by the CSF 390. But CI coefficients shows that it is the root 1 (not 3!)that has the highest CSF798 contribution. The CSF390 contribution is the highest in root 6 (this time agreeing with the CISelect). Furthermore, the printed overlaps (0.415 and 0.572) are not consistent in any way with CI coefficients from expansion of roots number 1 and 6, which are 0.86725 and -0.90987. (The coefficient for CSF798 in root 3 is zero!) : The output (not converged, because these are just testing calculations for proper root selection -- I believe this is not the reason of problem) is as follows: : RASSCF iterations: Energy and convergence statistics : ---------------------------------------------------- : : Iter CI SX CI RASSCF Energy max BLB max BLB max ROT Level Ln srch Step QN Time(min) : iter iter root energy change element value param shift minimum type update CPU : 1 1 6 0 -2756.13728258 0.00E+00 107 264 1 -0.57E-02 0.21E+00 0.93 0.00 SX NO 24.34 : No convergence in the CI section: MAXJT will be increased to : 52 : new roots selected: 2 15 : overlap 0.414 0.478 : 2 50 26 0 -2756.06496758 0.72E-01 99 110 1 -0.19E-01 0.21E+00 0.94 0.00 LS NO 12.65 : new roots selected: 2 17 : overlap 0.415 0.673 : 3 12 27 0 -2756.05178221 0.13E-01 108 174 1 0.34E-01 0.20E+00 0.93 0.06 LS NO 12.44 : new roots selected: 2 20 : overlap 0.414 0.471 : 4 11 19 0 -2756.04241535 0.94E-02 59 108 1 0.34E-01 0.30E+00 0.93 -0.50 LS NO 12.42 : new roots selected: 2 19 : overlap 0.415 0.698 : 5 38 28 0 -2756.05300894 -0.11E-01 108 174 1 0.38E-01 0.44E+00 0.93 2.50 LS NO 12.62 : new roots selected: 2 19 : overlap 0.415 0.700 : 6 10 30 0 -2756.05265003 0.36E-03 108 174 1 0.38E-01 -0.45E-01 0.93 0.40 SX NO 12.42 : No convergence in the CI section: MAXJT will be increased to : 54 : new roots selected: 3 10 : overlap 0.415 0.545 : 7 52 10 0 -2756.07254002 -0.20E-01 107 166 1 -0.76E-02 0.48E-01 0.93 1.08 QN YES 12.54 : new roots selected: 3 6 : overlap 0.416 0.596 : 8 53 10 0 -2756.07900970 -0.65E-02 59 117 1 0.78E-02 0.61E-01 0.93 1.05 QN YES 12.59 : new roots selected: 3 6 : overlap 0.415 0.612 : 9 43 12 0 -2756.08131850 -0.23E-02 107 166 1 0.70E-02 -0.28E-01 0.93 1.10 QN YES 12.52 : new roots selected: 3 6 : overlap 0.415 0.588 : 10 19 10 0 -2756.08262033 -0.13E-02 107 166 1 0.71E-02 -0.18E-01 0.93 1.63 LS YES 12.34 : No convergence after 10 iterations : new roots selected: 3 6 : overlap 0.415 0.572 : 11 14 10 0 -2756.08311313 -0.49E-03 107 166 1 0.71E-02 -0.18E-01 0.93 1.63 LS YES 12.28 : : ************************************************************************************************************************ : Wave function printout: : occupation of active orbitals, and spin coupling of open shells (u,d: Spin up or down) : ************************************************************************************************************************ : : : printout of CI-coefficients larger than 0.05 for root 1 : energy= -2756.163895 : conf/sym 11111111 Coeff Weight : 483 u2202200 -0.05394 0.00291 : 798 uu2d2200 -0.93126 0.86725 : 803 uu2d2020 0.09218 0.00850 : 806 uu2d0220 0.09002 0.00810 : 810 uu2ddudu 0.06934 0.00481 : 821 uu2duudd 0.13786 0.01900 : 824 uu2d2002 0.08112 0.00658 : 827 uu2d0202 0.09044 0.00818 : 1043 u0222200 0.09606 0.00923 : 1631 uu20220d 0.22328 0.04985 : : printout of CI-coefficients larger than 0.05 for root 2 : energy= -2756.126110 : conf/sym 11111111 Coeff Weight : 390 uu22d200 -0.10287 0.01058 : 1008 uud22200 -0.91622 0.83947 : 1013 uud22020 0.09109 0.00830 : 1016 uud20220 0.08653 0.00749 : 1020 uud2dudu 0.07109 0.00505 : 1031 uud2uudd 0.13779 0.01899 : 1034 uud22002 0.08505 0.00723 : 1037 uud20202 0.09108 0.00829 : 1336 uudd220u 0.13708 0.01879 : 1775 uudu220d 0.24385 0.05946 : : printout of CI-coefficients larger than 0.05 for root 3 : energy= -2756.094782 : conf/sym 11111111 Coeff Weight : 623 202u2200 0.25924 0.06721 : 658 ud2u2200 0.86144 0.74207 : 663 ud2u2020 -0.08526 0.00727 : 666 ud2u0220 -0.08326 0.00693 : 670 ud2ududu -0.07313 0.00535 : 681 ud2uuudd -0.12188 0.01486 : 684 ud2u2002 -0.07505 0.00563 : 687 ud2u0202 -0.08363 0.00699 : 693 022u2200 -0.25906 0.06711 : 1043 u0222200 -0.05666 0.00321 : 1176 2020220u -0.06156 0.00379 : 1196 ud20220u -0.20455 0.04184 : 1216 0220220u 0.06153 0.00379 : : printout of CI-coefficients larger than 0.05 for root 4 : energy= -2756.094692 : conf/sym 11111111 Coeff Weight : 623 202u2200 0.61427 0.37733 : 628 202u2020 -0.06077 0.00369 : 631 202u0220 -0.05933 0.00352 : 635 202ududu -0.05214 0.00272 : 646 202uuudd -0.08691 0.00755 : 649 202u2002 -0.05356 0.00287 : 652 202u0202 -0.05963 0.00356 : 658 ud2u2200 -0.36648 0.13431 : 681 ud2uuudd 0.05185 0.00269 : 693 022u2200 -0.60393 0.36473 : 698 022u2020 0.05980 0.00358 : 701 022u0220 0.05841 0.00341 : 705 022ududu 0.05127 0.00263 : 716 022uuudd 0.08545 0.00730 : 719 022u2002 0.05258 0.00276 : 722 022u0202 0.05864 0.00344 : 1078 0u222200 0.05672 0.00322 : 1176 2020220u -0.14633 0.02141 : 1196 ud20220u 0.08704 0.00758 : 1216 0220220u 0.14295 0.02044 : : printout of CI-coefficients larger than 0.05 for root 5 : energy= -2756.072865 : conf/sym 11111111 Coeff Weight : 389 uu222d00 0.92870 0.86248 : 397 uu220d20 0.09997 0.00999 : 407 uu22u0dd -0.11830 0.01399 : 411 uu220d02 0.07856 0.00617 : 800 uu2dd2u0 -0.06420 0.00412 : 807 uu2d2d0u -0.06689 0.00447 : 815 uu2d2u0d 0.07049 0.00497 : 1546 uu2ud2d0 0.11199 0.01254 : 1549 uu2u2d0d 0.22578 0.05098 : 1640 uu202d02 0.12243 0.01499 : : printout of CI-coefficients larger than 0.05 for root 6 : energy= -2756.071444 : conf/sym 11111111 Coeff Weight : 390 uu22d200 -0.90987 0.82787 : 396 uu22d020 0.09761 0.00953 : 408 uu220udd 0.11726 0.01375 : 410 uu22d002 0.06725 0.00452 : 799 uu2d2du0 -0.06934 0.00481 : 808 uu2dd20u 0.06762 0.00457 : 816 uu2du20d -0.08121 0.00660 : 1008 uud22200 0.06097 0.00372 : 1336 uudd220u -0.05733 0.00329 : 1545 uu2u2dd0 0.13215 0.01746 : 1550 uu2ud20d -0.23719 0.05626 : 1641 uu20d202 -0.12293 0.01511 : 1775 uudu220d -0.11848 0.01404 :

[ Follow Ups ] [ Post Followup ] [ Molcas user's WWWBoard ]