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You can choose an avatar and change the default style by going to "Profile" → "Personality" or "Display".#1 2023-11-12 07:04:20
- ABQTrap
- Member
- Registered: 2023-03-19
- Posts: 21
Is it OK if denominators of CASPT2 had small negative values?
Dear all,
I tried to perform geometrical optimization using CASPT2 on top of RASSCF. The targed state is the ground state, but I did state-average RASSCF calculations of five states to include four excited states. From the &CASPT2 part of the output file, I found that the fourth excited state had several denominators with negative values, while other denominators are all positive, the openmolcas program ended with "Happy Landing" without warning. The reference weights seem to be OK, the value is round 0.66 (molecular system has 70 electrons).
My question is, should I worried about the intruder state problem? Is there any keywords to set to prevent the negative values and improve geometrical convergence? I already used the imaginary shift of 0.2. Thanks a lot.
++ CASPT2 computation for group 5
********************************************************************************
Multi-State initialization phase begins for group 5
--------------------------------------------------------------------------------
********************************************************************************
Compute H0 matrices for state 5
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
H0 matrices have been computed.
********************************************************************************
CASPT2 EQUATION SOLUTION
--------------------------------------------------------------------------------
Total nr of CASPT2 parameters:
Before reduction: 112147110
After reduction: 112139310
Variance of |WF0>: 15.6575134384
The contributions to the second order correlation energy in atomic units.
-----------------------------------------------------------------------------------------------------------------------------
IT. VJTU VJTI ATVX AIVX VJAI BVAT BJAT BJAI TOTAL RNORM
-----------------------------------------------------------------------------------------------------------------------------
1 -0.000125 -0.000456 -0.029425 -0.104554 -0.051577 -0.073630 -0.316880 -1.215757 -1.792405 0.003324
2 -0.000128 -0.000457 -0.029533 -0.104622 -0.051603 -0.073688 -0.316976 -1.215817 -1.792824 0.000330
3 -0.000129 -0.000457 -0.029538 -0.104632 -0.051606 -0.073692 -0.316984 -1.215819 -1.792856 0.000048
4 -0.000129 -0.000457 -0.029537 -0.104630 -0.051606 -0.073691 -0.316983 -1.215818 -1.792851 0.000005
-----------------------------------------------------------------------------------------------------------------------------
FINAL CASPT2 RESULT:
Reference energy: -434.1750795085
E2 (Non-variational): -1.7928505221
Shift correction: -0.0080523913
E2 (Variational): -1.8009029134
Total energy: -435.9759824219
Residual norm: 0.0000006768
Reference weight: 0.66591
Contributions to the CASPT2 correlation energy
Active & Virtual Only: -0.1032278103
One Inactive Excited: -0.4217416549
Two Inactive Excited: -1.2678810568
++ Denominators, etc.
--------------------------------------------------------------------------------------------------------------
Report on small energy denominators, large coefficients, and large energy contributions.
CASE SYMM ACTIVE-MIX NON-ACTIVE INDICES DENOMINATOR RHS VALUE COEFFICIENT CONTRIBUTION
VJTU 1 Mu1.0001 In1.017 0.28880277 0.00000847 -0.00004070 -0.00000000
VJTU 1 Mu1.0001 In1.018 0.21810718 0.00003665 -0.00009541 -0.00000000
VJTU 1 Mu1.0002 In1.018 0.25631708 -0.00000003 0.00000006 -0.00000000
VJTU 1 Mu1.0001 In1.019 0.13080632 -0.00000207 -0.00000256 0.00000000
VJTU 1 Mu1.0002 In1.019 0.16901622 0.00000000 -0.00000000 -0.00000000
VJTU 1 Mu1.0003 In1.019 0.27830616 0.00000000 -0.00000001 -0.00000000
VJTU 1 Mu1.0001 In1.020 0.09734985 0.00000003 -0.00000005 -0.00000000
VJTU 1 Mu1.0002 In1.020 0.13555975 0.00000751 -0.00002403 -0.00000000
VJTU 1 Mu1.0003 In1.020 0.24484969 0.00000265 -0.00000833 -0.00000000
VJTU 1 Mu1.0004 In1.020 0.28305961 0.00000006 -0.00000005 -0.00000000
VJTU 1 Mu1.0005 In1.020 0.28305961 -0.00000004 0.00000012 -0.00000000
VJTU 1 Mu1.0006 In1.020 0.28305971 -0.00000000 0.00000000 -0.00000000
VJTU 1 Mu1.0001 In1.021 0.07901691 0.00002544 -0.00003773 -0.00000000
VJTU 1 Mu1.0002 In1.021 0.11722682 0.00000000 -0.00000002 -0.00000000
VJTU 1 Mu1.0003 In1.021 0.22651676 0.00000001 -0.00000004 -0.00000000
VJTU 1 Mu1.0004 In1.021 0.26472667 0.00025261 -0.00038356 -0.00000010
VJTU 1 Mu1.0005 In1.021 0.26472667 -0.00044736 0.00122665 -0.00000055
VJTU 1 Mu1.0006 In1.021 0.26472677 0.00000503 -0.00001329 -0.00000000
VJTU 1 Mu1.0001 In1.022 0.06779773 0.00007527 -0.00012114 -0.00000001
VJTU 1 Mu1.0002 In1.022 0.10600763 -0.00000003 0.00000007 -0.00000000
VJTU 1 Mu1.0003 In1.022 0.21529757 0.00000001 -0.00000001 -0.00000000
VJTU 1 Mu1.0004 In1.022 0.25350749 0.00044728 -0.00086285 -0.00000039
VJTU 1 Mu1.0005 In1.022 0.25350749 -0.00058970 0.00164814 -0.00000097
VJTU 1 Mu1.0006 In1.022 0.25350759 0.00000820 -0.00001832 -0.00000000
VJTU 1 Mu1.0007 In1.022 0.29171638 0.00000001 -0.00000003 -0.00000000
VJTU 1 Mu1.0001 In1.023 0.05229276 0.00000009 -0.00000011 -0.00000000
VJTU 1 Mu1.0002 In1.023 0.09050266 -0.00000157 0.00000464 -0.00000000
VJTU 1 Mu1.0003 In1.023 0.19979260 0.00000055 -0.00000070 -0.00000000
VJTU 1 Mu1.0004 In1.023 0.23800252 0.00000035 -0.00000090 -0.00000000
VJTU 1 Mu1.0005 In1.023 0.23800252 -0.00000020 0.00000048 -0.00000000
VJTU 1 Mu1.0006 In1.023 0.23800262 -0.00000001 0.00000002 -0.00000000
VJTU 1 Mu1.0007 In1.023 0.27621141 -0.00000056 0.00000172 -0.00000000
VJTU 1 Mu1.0001 In1.024 0.03232783 -0.00000765 0.00000575 -0.00000000
VJTU 1 Mu1.0002 In1.024 0.07053773 0.00000016 -0.00000025 -0.00000000
VJTU 1 Mu1.0003 In1.024 0.17982767 0.00000001 -0.00000003 -0.00000000
VJTU 1 Mu1.0004 In1.024 0.21803759 0.00019409 -0.00031914 -0.00000006
VJTU 1 Mu1.0005 In1.024 0.21803759 -0.00034730 0.00114587 -0.00000040
VJTU 1 Mu1.0006 In1.024 0.21803768 0.00002186 -0.00006170 -0.00000000
VJTU 1 Mu1.0007 In1.024 0.25624648 0.00000003 -0.00000007 -0.00000000
VJTU 1 Mu1.0001 In1.025 0.00497187 0.00009781 -0.00001097 -0.00000000
VJTU 1 Mu1.0002 In1.025 0.04318177 -0.00000031 0.00000031 -0.00000000
VJTU 1 Mu1.0003 In1.025 0.15247171 0.00000001 -0.00000003 -0.00000000
VJTU 1 Mu1.0004 In1.025 0.19068162 0.00025277 0.00009697 0.00000002
VJTU 1 Mu1.0005 In1.025 0.19068162 -0.00043141 0.00110258 -0.00000048
VJTU 1 Mu1.0006 In1.025 0.19068172 -0.00002476 0.00006831 -0.00000000
VJTU 1 Mu1.0007 In1.025 0.22889052 -0.00000004 0.00000009 -0.00000000
VJTU 1 Mu1.0001 In1.026 -0.01472939 -0.00000001 -0.00000000 0.00000000
VJTU 1 Mu1.0002 In1.026 0.02348051 0.00000142 -0.00000067 -0.00000000
VJTU 1 Mu1.0003 In1.026 0.13277045 -0.00000126 0.00000414 -0.00000000
VJTU 1 Mu1.0004 In1.026 0.17098037 -0.00000000 0.00000037 -0.00000000
VJTU 1 Mu1.0005 In1.026 0.17098037 0.00000006 -0.00000019 -0.00000000
VJTU 1 Mu1.0006 In1.026 0.17098047 -0.00000001 0.00000004 -0.00000000
VJTU 1 Mu1.0007 In1.026 0.20918926 0.00000041 -0.00000144 -0.00000000
VJTU 1 Mu1.0001 In1.027 -0.02557642 -0.00002590 -0.00001579 0.00000000
VJTU 1 Mu1.0002 In1.027 0.01263349 0.00000005 -0.00000002 -0.00000000
VJTU 1 Mu1.0003 In1.027 0.12192343 -0.00000000 0.00000000 -0.00000000
VJTU 1 Mu1.0004 In1.027 0.16013334 -0.00040573 0.00086799 -0.00000035
VJTU 1 Mu1.0005 In1.027 0.16013334 -0.00009420 0.00018693 -0.00000002
VJTU 1 Mu1.0006 In1.027 0.16013344 0.00000088 -0.00000274 -0.00000000
VJTU 1 Mu1.0007 In1.027 0.19834223 0.00000000 -0.00000000 -0.00000000
VJTU 1 Mu1.0001 In1.028 -0.04216829 0.00000006 0.00000006 0.00000000
VJTU 1 Mu1.0002 In1.028 -0.00395838 -0.00000606 -0.00000082 0.00000000
VJTU 1 Mu1.0003 In1.028 0.10533156 -0.00000107 0.00000328 -0.00000000
VJTU 1 Mu1.0004 In1.028 0.14354147 0.00000032 -0.00000090 -0.00000000
VJTU 1 Mu1.0005 In1.028 0.14354147 -0.00000020 0.00000053 -0.00000000
VJTU 1 Mu1.0006 In1.028 0.14354157 0.00000000 -0.00000000 -0.00000000
VJTU 1 Mu1.0007 In1.028 0.18175036 -0.00000034 0.00000113 -0.00000000
VJTU 1 Mu1.0008 In1.028 0.29104133 0.00000263 -0.00001623 -0.00000000
VJTU 1 Mu1.0001 In1.029 -0.05797322 -0.00000002 -0.00000003 0.00000000
VJTU 1 Mu1.0002 In1.029 -0.01976332 -0.00000084 -0.00000094 0.00000000
VJTU 1 Mu1.0003 In1.029 0.08952662 -0.00000179 0.00000504 -0.00000000
VJTU 1 Mu1.0004 In1.029 0.12773654 0.00000005 0.00000001 0.00000000
VJTU 1 Mu1.0005 In1.029 0.12773654 0.00000011 -0.00000026 -0.00000000
VJTU 1 Mu1.0006 In1.029 0.12773663 -0.00000000 0.00000000 -0.00000000
VJTU 1 Mu1.0007 In1.029 0.16594543 0.00000021 -0.00000099 -0.00000000
VJTU 1 Mu1.0008 In1.029 0.27523639 0.00006032 -0.00016072 -0.00000001
VJTU 1 Mu1.0009 In1.029 0.28785777 0.00002720 -0.00007011 -0.00000000
VJTU 1 Mu1.0001 In1.030 -0.06908386 -0.00002109 -0.00003273 0.00000000
VJTU 1 Mu1.0002 In1.030 -0.03087396 0.00000002 0.00000002 0.00000000
VJTU 1 Mu1.0003 In1.030 0.07841598 -0.00000001 0.00000002 -0.00000000
VJTU 1 Mu1.0004 In1.030 0.11662590 0.00029409 -0.00066603 -0.00000020
VJTU 1 Mu1.0005 In1.030 0.11662590 0.00015385 -0.00030296 -0.00000005
VJTU 1 Mu1.0006 In1.030 0.11662600 0.00000385 -0.00000952 -0.00000000
VJTU 1 Mu1.0007 In1.030 0.15483479 0.00000001 -0.00000003 -0.00000000
VJTU 1 Mu1.0008 In1.030 0.26412576 0.00000100 -0.00000269 -0.00000000
VJTU 1 Mu1.0009 In1.030 0.27674713 0.00000061 -0.00000185 -0.00000000
VJTU 1 Mu1.0010 In1.030 0.29234363 -0.00000064 0.00000191 -0.00000000
VJTU 1 Mu1.0001 In1.031 -0.07496795 -0.00000000 -0.00000003 0.00000000
VJTU 1 Mu1.0002 In1.031 -0.03675804 -0.00001581 -0.00001570 0.00000000
VJTU 1 Mu1.0003 In1.031 0.07253190 -0.00000592 0.00000808 -0.00000000
VJTU 1 Mu1.0004 In1.031 0.11074181 -0.00000040 0.00000101 -0.00000000
VJTU 1 Mu1.0005 In1.031 0.11074181 -0.00000031 0.00000042 -0.00000000
VJTU 1 Mu1.0006 In1.031 0.11074191 -0.00000001 0.00000004 -0.00000000
VJTU 1 Mu1.0007 In1.031 0.14895070 0.00000115 -0.00000259 -0.00000000
VJTU 1 Mu1.0008 In1.031 0.25824167 0.00029807 -0.00081178 -0.00000024
VJTU 1 Mu1.0009 In1.031 0.27086304 0.00016941 -0.00053074 -0.00000009
VJTU 1 Mu1.0010 In1.031 0.28645954 -0.00017899 0.00054440 -0.00000010
VJTU 1 Mu1.0011 In1.031 0.29645158 0.00000007 -0.00000017 -0.00000000
ATVX 1 Mu1.0001 Se1.038 -0.16556821 -0.00000000 0.00000001 -0.00000000
ATVX 1 Mu1.0002 Se1.038 -0.04554818 -0.00002985 -0.00002553 0.00000000
ATVX 1 Mu1.0003 Se1.038 -0.00685804 0.00000072 0.00000011 0.00000000
ATVX 1 Mu1.0004 Se1.038 0.01057323 -0.00000046 0.00000014 -0.00000000
ATVX 1 Mu1.0005 Se1.038 0.03857183 0.00000022 -0.00000021 -0.00000000
ATVX 1 Mu1.0006 Se1.038 0.15293623 0.00013822 -0.00023293 -0.00000003
ATVX 1 Mu1.0007 Se1.038 0.15391565 -0.00001942 0.00000944 -0.00000000
ATVX 1 Mu1.0008 Se1.038 0.16435453 -0.00001144 -0.00002926 0.00000000
ATVX 1 Mu1.0009 Se1.038 0.16858386 0.00013615 -0.00025929 -0.00000004
ATVX 1 Mu1.0010 Se1.038 0.17595225 -0.00000009 0.00002540 -0.00000000
ATVX 1 Mu1.0011 Se1.038 0.19119302 -0.00000139 0.00000232 -0.00000000
ATVX 1 Mu1.0012 Se1.038 0.19591850 -0.00000012 0.00000033 -0.00000000
ATVX 1 Mu1.0013 Se1.038 0.20432304 0.00000216 -0.00000413 -0.00000000
ATVX 1 Mu1.0014 Se1.038 0.20673549 -0.00000074 0.00000083 -0.00000000
ATVX 1 Mu1.0015 Se1.038 0.22340285 -0.00000020 0.00000045 -0.00000000
ATVX 1 Mu1.0016 Se1.038 0.27588955 0.00000369 -0.00000967 -0.00000000
ATVX 1 Mu1.0017 Se1.038 0.28325206 0.00000012 -0.00000033 -0.00000000
ATVX 1 Mu1.0001 Se1.039 -0.14368003 -0.00000004 -0.00000006 0.00000000
ATVX 1 Mu1.0002 Se1.039 -0.02366000 0.00030370 0.00016180 0.00000005
ATVX 1 Mu1.0003 Se1.039 0.01503014 0.00000146 -0.00000050 -0.00000000
ATVX 1 Mu1.0004 Se1.039 0.03246142 -0.00000131 0.00000117 -0.00000000
ATVX 1 Mu1.0005 Se1.039 0.06046001 0.00000059 -0.00000087 -0.00000000
ATVX 1 Mu1.0006 Se1.039 0.17482441 0.00002144 -0.00060349 -0.00000001
ATVX 1 Mu1.0007 Se1.039 0.17580383 0.00014969 -0.00042135 -0.00000006
ATVX 1 Mu1.0008 Se1.039 0.18624272 0.00022943 -0.00054203 -0.00000012
ATVX 1 Mu1.0009 Se1.039 0.19047204 0.00037102 -0.00144157 -0.00000053
ATVX 1 Mu1.0010 Se1.039 0.19784043 -0.00010129 0.00024007 -0.00000002
ATVX 1 Mu1.0011 Se1.039 0.21308120 -0.00000321 0.00000507 -0.00000000
ATVX 1 Mu1.0012 Se1.039 0.21780668 -0.00000040 0.00000096 -0.00000000
ATVX 1 Mu1.0013 Se1.039 0.22621122 0.00004464 -0.00010035 -0.00000000
ATVX 1 Mu1.0014 Se1.039 0.22862367 -0.00000194 0.00000222 -0.00000000
ATVX 1 Mu1.0015 Se1.039 0.24529103 -0.00000054 0.00000131 -0.00000000
ATVX 1 Mu1.0016 Se1.039 0.29777773 -0.00005644 0.00012855 -0.00000001
ATVX 1 Mu1.0001 Se1.040 -0.12648650 0.00000608 0.00001020 0.00000000
ATVX 1 Mu1.0002 Se1.040 -0.00646647 0.00000040 0.00000006 0.00000000
ATVX 1 Mu1.0003 Se1.040 0.03222367 -0.00025697 0.00018726 -0.00000005
ATVX 1 Mu1.0004 Se1.040 0.04965494 0.00016574 -0.00022291 -0.00000004
ATVX 1 Mu1.0005 Se1.040 0.07765354 -0.00008202 0.00014670 -0.00000001
ATVX 1 Mu1.0006 Se1.040 0.19201794 0.00000027 -0.00000127 -0.00000000
ATVX 1 Mu1.0007 Se1.040 0.19299736 0.00000028 -0.00000072 -0.00000000
ATVX 1 Mu1.0008 Se1.040 0.20343624 0.00000015 -0.00000035 -0.00000000
ATVX 1 Mu1.0009 Se1.040 0.20766557 0.00000067 -0.00000221 -0.00000000
ATVX 1 Mu1.0010 Se1.040 0.21503395 -0.00000042 0.00000090 -0.00000000
ATVX 1 Mu1.0011 Se1.040 0.23027473 0.00052672 -0.00079112 -0.00000042
ATVX 1 Mu1.0012 Se1.040 0.23500021 0.00004522 -0.00009409 -0.00000000
ATVX 1 Mu1.0013 Se1.040 0.24340475 0.00000019 -0.00000057 -0.00000000
ATVX 1 Mu1.0014 Se1.040 0.24581720 0.00030604 -0.00029741 -0.00000009
ATVX 1 Mu1.0015 Se1.040 0.26248456 0.00008079 -0.00019367 -0.00000002
ATVX 1 Mu1.0001 Se1.041 -0.12113656 0.00000003 0.00000004 0.00000000
ATVX 1 Mu1.0002 Se1.041 -0.00111653 -0.00006142 -0.00000146 0.00000000
ATVX 1 Mu1.0003 Se1.041 0.03757362 -0.00000170 0.00000143 -0.00000000
ATVX 1 Mu1.0004 Se1.041 0.05500489 0.00000145 -0.00000209 -0.00000000
ATVX 1 Mu1.0005 Se1.041 0.08300348 -0.00000065 0.00000123 -0.00000000
ATVX 1 Mu1.0006 Se1.041 0.19736788 0.00047064 -0.00106723 -0.00000050
ATVX 1 Mu1.0007 Se1.041 0.19834730 0.00027055 -0.00068839 -0.00000019
ATVX 1 Mu1.0008 Se1.041 0.20878619 0.00013319 -0.00037088 -0.00000005
ATVX 1 Mu1.0009 Se1.041 0.21301551 0.00037618 -0.00083310 -0.00000031
ATVX 1 Mu1.0010 Se1.041 0.22038390 -0.00005546 0.00015882 -0.00000001
ATVX 1 Mu1.0011 Se1.041 0.23562467 0.00000247 -0.00000263 -0.00000000
ATVX 1 Mu1.0012 Se1.041 0.24035015 -0.00000024 0.00000080 -0.00000000
ATVX 1 Mu1.0013 Se1.041 0.24875469 -0.00008155 0.00020019 -0.00000002
ATVX 1 Mu1.0014 Se1.041 0.25116714 0.00000101 0.00000057 0.00000000
ATVX 1 Mu1.0015 Se1.041 0.26783450 0.00000076 -0.00000187 -0.00000000
ATVX 1 Mu1.0001 Se1.042 -0.10639160 0.00000004 0.00000006 0.00000000
ATVX 1 Mu1.0002 Se1.042 0.01362843 -0.00016723 0.00005114 -0.00000001
ATVX 1 Mu1.0003 Se1.042 0.05231857 -0.00000158 0.00000180 -0.00000000
ATVX 1 Mu1.0004 Se1.042 0.06974984 0.00000119 -0.00000211 -0.00000000
ATVX 1 Mu1.0005 Se1.042 0.09774844 -0.00000057 0.00000118 -0.00000000
ATVX 1 Mu1.0006 Se1.042 0.21211283 0.00001182 0.00032199 0.00000000
ATVX 1 Mu1.0007 Se1.042 0.21309225 -0.00015004 0.00038345 -0.00000006
ATVX 1 Mu1.0008 Se1.042 0.22353114 -0.00020453 0.00046681 -0.00000010
ATVX 1 Mu1.0009 Se1.042 0.22776047 -0.00016759 0.00072772 -0.00000012
ATVX 1 Mu1.0010 Se1.042 0.23512885 0.00009479 -0.00021754 -0.00000002
ATVX 1 Mu1.0011 Se1.042 0.25036962 0.00000349 -0.00000563 -0.00000000
ATVX 1 Mu1.0012 Se1.042 0.25509510 0.00000041 -0.00000087 -0.00000000
ATVX 1 Mu1.0013 Se1.042 0.26349964 -0.00002335 0.00005219 -0.00000000
ATVX 1 Mu1.0014 Se1.042 0.26591210 0.00000207 -0.00000247 -0.00000000
ATVX 1 Mu1.0015 Se1.042 0.28257946 0.00000053 -0.00000126 -0.00000000
ATVX 1 Mu1.0001 Se1.043 -0.10307600 -0.00000291 -0.00000240 0.00000000
ATVX 1 Mu1.0002 Se1.043 0.01694403 -0.00000008 0.00000003 -0.00000000
ATVX 1 Mu1.0003 Se1.043 0.05563417 0.00019252 -0.00022835 -0.00000004
ATVX 1 Mu1.0004 Se1.043 0.07306544 -0.00015034 0.00027788 -0.00000004
ATVX 1 Mu1.0005 Se1.043 0.10106404 0.00006927 -0.00014842 -0.00000001
ATVX 1 Mu1.0006 Se1.043 0.21542844 -0.00000005 0.00000046 -0.00000000
ATVX 1 Mu1.0007 Se1.043 0.21640785 -0.00000023 0.00000058 -0.00000000
ATVX 1 Mu1.0008 Se1.043 0.22684674 -0.00000010 0.00000022 -0.00000000
ATVX 1 Mu1.0009 Se1.043 0.23107607 -0.00000020 0.00000078 -0.00000000
ATVX 1 Mu1.0010 Se1.043 0.23844445 0.00000032 -0.00000069 -0.00000000
ATVX 1 Mu1.0011 Se1.043 0.25368523 -0.00038922 0.00055768 -0.00000022
ATVX 1 Mu1.0012 Se1.043 0.25841071 -0.00003484 0.00007480 -0.00000000
ATVX 1 Mu1.0013 Se1.043 0.26681524 -0.00000012 0.00000039 -0.00000000
ATVX 1 Mu1.0014 Se1.043 0.26922770 -0.00021562 0.00017920 -0.00000004
ATVX 1 Mu1.0015 Se1.043 0.28589506 -0.00006392 0.00015299 -0.00000001
ATVX 1 Mu1.0001 Se1.044 -0.09298493 -0.00000003 -0.00000004 0.00000000
ATVX 1 Mu1.0002 Se1.044 0.02703510 0.00034900 -0.00021273 -0.00000007
ATVX 1 Mu1.0003 Se1.044 0.06572524 0.00000085 -0.00000117 -0.00000000
ATVX 1 Mu1.0004 Se1.044 0.08315651 -0.00000094 0.00000187 -0.00000000
ATVX 1 Mu1.0005 Se1.044 0.11115511 0.00000040 -0.00000089 -0.00000000
ATVX 1 Mu1.0006 Se1.044 0.22551951 -0.00046968 0.00054279 -0.00000025
ATVX 1 Mu1.0007 Se1.044 0.22649893 -0.00011424 0.00027287 -0.00000003
ATVX 1 Mu1.0008 Se1.044 0.23693782 0.00006505 -0.00008021 -0.00000001
ATVX 1 Mu1.0009 Se1.044 0.24116714 -0.00009697 -0.00031549 0.00000003
ATVX 1 Mu1.0010 Se1.044 0.24853553 -0.00003054 0.00004136 -0.00000000
ATVX 1 Mu1.0011 Se1.044 0.26377630 -0.00000162 0.00000220 -0.00000000
ATVX 1 Mu1.0012 Se1.044 0.26850178 -0.00000001 -0.00000003 0.00000000
ATVX 1 Mu1.0013 Se1.044 0.27690632 0.00008980 -0.00020550 -0.00000002
ATVX 1 Mu1.0014 Se1.044 0.27931877 -0.00000095 0.00000077 -0.00000000
ATVX 1 Mu1.0015 Se1.044 0.29598613 -0.00000043 0.00000100 -0.00000000
ATVX 1 Mu1.0001 Se1.045 -0.08363460 0.00001477 0.00001673 0.00000000
ATVX 1 Mu1.0002 Se1.045 0.03638543 0.00000097 -0.00000078 -0.00000000
ATVX 1 Mu1.0003 Se1.045 0.07507557 -0.00077098 0.00117397 -0.00000091
ATVX 1 Mu1.0004 Se1.045 0.09250685 0.00056189 -0.00122329 -0.00000069
ATVX 1 Mu1.0005 Se1.045 0.12050544 -0.00026540 0.00062208 -0.00000017
ATVX 1 Mu1.0006 Se1.045 0.23486984 -0.00000050 -0.00000063 0.00000000
ATVX 1 Mu1.0007 Se1.045 0.23584926 0.00000032 -0.00000081 -0.00000000
ATVX 1 Mu1.0008 Se1.045 0.24628815 0.00000008 -0.00000005 -0.00000000
ATVX 1 Mu1.0009 Se1.045 0.25051747 0.00000058 -0.00000301 -0.00000000
ATVX 1 Mu1.0010 Se1.045 0.25788586 -0.00000104 0.00000208 -0.00000000
ATVX 1 Mu1.0011 Se1.045 0.27312663 0.00151127 -0.00208443 -0.00000315
ATVX 1 Mu1.0012 Se1.045 0.27785211 0.00005315 -0.00006312 -0.00000000
ATVX 1 Mu1.0013 Se1.045 0.28625665 0.00000065 -0.00000185 -0.00000000
ATVX 1 Mu1.0014 Se1.045 0.28866910 0.00083434 -0.00063190 -0.00000053
ATVX 1 Mu1.0001 Se1.046 -0.07349182 -0.00000002 -0.00000003 0.00000000
ATVX 1 Mu1.0002 Se1.046 0.04652821 0.00008899 -0.00009094 -0.00000001
ATVX 1 Mu1.0003 Se1.046 0.08521835 0.00000053 -0.00000092 -0.00000000
ATVX 1 Mu1.0004 Se1.046 0.10264962 -0.00000025 0.00000054 -0.00000000
ATVX 1 Mu1.0005 Se1.046 0.13064822 0.00000014 -0.00000033 -0.00000000
ATVX 1 Mu1.0006 Se1.046 0.24501262 0.00009881 -0.00039504 -0.00000004
ATVX 1 Mu1.0007 Se1.046 0.24599204 0.00012561 -0.00029464 -0.00000004
ATVX 1 Mu1.0008 Se1.046 0.25643093 0.00010535 -0.00021648 -0.00000002
ATVX 1 Mu1.0009 Se1.046 0.26066025 0.00014713 -0.00047672 -0.00000007
ATVX 1 Mu1.0010 Se1.046 0.26802864 -0.00004530 0.00009300 -0.00000000
ATVX 1 Mu1.0011 Se1.046 0.28326941 -0.00000153 0.00000307 -0.00000000
ATVX 1 Mu1.0012 Se1.046 0.28799489 -0.00000020 0.00000043 -0.00000000
ATVX 1 Mu1.0013 Se1.046 0.29639943 -0.00000795 0.00001821 -0.00000000
ATVX 1 Mu1.0014 Se1.046 0.29881188 -0.00000115 0.00000223 -0.00000000
ATVX 1 Mu1.0001 Se1.047 -0.07035730 0.00000004 0.00000005 0.00000000
ATVX 1 Mu1.0002 Se1.047 0.04966273 -0.00023644 0.00025422 -0.00000006
ATVX 1 Mu1.0003 Se1.047 0.08835287 -0.00000168 0.00000290 -0.00000000
ATVX 1 Mu1.0004 Se1.047 0.10578414 0.00000144 -0.00000333 -0.00000000
ATVX 1 Mu1.0005 Se1.047 0.13378274 -0.00000066 0.00000162 -0.00000000
ATVX 1 Mu1.0006 Se1.047 0.24814714 -0.00016662 0.00082303 -0.00000014
ATVX 1 Mu1.0007 Se1.047 0.24912655 -0.00024190 0.00063399 -0.00000015
ATVX 1 Mu1.0008 Se1.047 0.25956544 -0.00027541 0.00064492 -0.00000018
ATVX 1 Mu1.0009 Se1.047 0.26379477 -0.00045820 0.00148459 -0.00000068
ATVX 1 Mu1.0010 Se1.047 0.27116315 0.00012190 -0.00028054 -0.00000003
ATVX 1 Mu1.0011 Se1.047 0.28640393 0.00000344 -0.00000508 -0.00000000
ATVX 1 Mu1.0012 Se1.047 0.29112941 0.00000050 -0.00000108 -0.00000000
ATVX 1 Mu1.0013 Se1.047 0.29953394 -0.00002194 0.00004430 -0.00000000
ATVX 1 Mu1.0001 Se1.048 -0.06430443 -0.00000035 -0.00000288 0.00000000
ATVX 1 Mu1.0002 Se1.048 0.05571560 -0.00000068 0.00000085 -0.00000000
ATVX 1 Mu1.0003 Se1.048 0.09440574 -0.00011621 0.00019896 -0.00000002
ATVX 1 Mu1.0004 Se1.048 0.11183701 0.00013614 -0.00032646 -0.00000004
ATVX 1 Mu1.0005 Se1.048 0.13983561 -0.00005587 0.00013947 -0.00000001
ATVX 1 Mu1.0006 Se1.048 0.25420001 0.00000016 0.00000015 0.00000000
ATVX 1 Mu1.0007 Se1.048 0.25517943 0.00000011 -0.00000029 -0.00000000
ATVX 1 Mu1.0008 Se1.048 0.26561832 -0.00000022 0.00000039 -0.00000000
ATVX 1 Mu1.0009 Se1.048 0.26984764 -0.00000034 0.00000127 -0.00000000
ATVX 1 Mu1.0010 Se1.048 0.27721603 -0.00000003 0.00000005 -0.00000000
ATVX 1 Mu1.0011 Se1.048 0.29245680 0.00016856 -0.00012832 -0.00000002
ATVX 1 Mu1.0012 Se1.048 0.29718228 -0.00002427 0.00007582 -0.00000000
ATVX 1 Mu1.0001 Se1.049 -0.04999148 -0.00000006 -0.00000005 0.00000000
ATVX 1 Mu1.0002 Se1.049 0.07002855 0.00028941 -0.00041036 -0.00000012
ATVX 1 Mu1.0003 Se1.049 0.10871869 0.00000265 -0.00000521 -0.00000000
ATVX 1 Mu1.0004 Se1.049 0.12614996 -0.00000193 0.00000493 -0.00000000
ATVX 1 Mu1.0005 Se1.049 0.15414856 0.00000092 -0.00000235 -0.00000000
ATVX 1 Mu1.0006 Se1.049 0.26851296 -0.00008021 -0.00037925 0.00000003
ATVX 1 Mu1.0007 Se1.049 0.26949237 0.00014670 -0.00038784 -0.00000006
ATVX 1 Mu1.0008 Se1.049 0.27993126 0.00022904 -0.00049532 -0.00000011
ATVX 1 Mu1.0009 Se1.049 0.28416059 0.00024048 -0.00106738 -0.00000026
ATVX 1 Mu1.0010 Se1.049 0.29152897 -0.00010976 0.00023980 -0.00000003
ATVX 1 Mu1.0001 Se1.050 -0.03305218 0.00000887 0.00000515 0.00000000
ATVX 1 Mu1.0002 Se1.050 0.08696785 0.00000033 -0.00000057 -0.00000000
ATVX 1 Mu1.0003 Se1.050 0.12565800 -0.00044178 0.00093010 -0.00000041
ATVX 1 Mu1.0004 Se1.050 0.14308927 0.00031504 -0.00084321 -0.00000027
ATVX 1 Mu1.0005 Se1.050 0.17108787 -0.00014950 0.00038965 -0.00000006
ATVX 1 Mu1.0006 Se1.050 0.28545226 -0.00000038 0.00000036 -0.00000000
ATVX 1 Mu1.0007 Se1.050 0.28643168 -0.00000015 0.00000037 -0.00000000
ATVX 1 Mu1.0008 Se1.050 0.29687057 -0.00000027 0.00000064 -0.00000000
ATVX 1 Mu1.0001 Se1.051 -0.01112288 0.00000001 0.00000000 0.00000000
ATVX 1 Mu1.0002 Se1.051 0.10889715 -0.00024975 0.00049100 -0.00000012
ATVX 1 Mu1.0003 Se1.051 0.14758729 -0.00000005 0.00000014 -0.00000000
ATVX 1 Mu1.0004 Se1.051 0.16501856 -0.00000011 0.00000033 -0.00000000
ATVX 1 Mu1.0005 Se1.051 0.19301716 0.00000003 -0.00000011 -0.00000000
ATVX 1 Mu1.0001 Se1.052 0.00916145 0.00000001 -0.00000000 -0.00000000
ATVX 1 Mu1.0002 Se1.052 0.12918148 0.00045475 -0.00096737 -0.00000044
ATVX 1 Mu1.0003 Se1.052 0.16787162 -0.00000159 0.00000373 -0.00000000
ATVX 1 Mu1.0004 Se1.052 0.18530289 0.00000084 -0.00000236 -0.00000000
ATVX 1 Mu1.0005 Se1.052 0.21330149 -0.00000043 0.00000113 -0.00000000
ATVX 1 Mu1.0001 Se1.053 0.00663183 -0.00000291 0.00000077 -0.00000000
ATVX 1 Mu1.0002 Se1.053 0.12665186 0.00000062 -0.00000124 -0.00000000
ATVX 1 Mu1.0003 Se1.053 0.16534200 -0.00008189 0.00017955 -0.00000001
ATVX 1 Mu1.0004 Se1.053 0.18277327 0.00013939 -0.00038724 -0.00000005
ATVX 1 Mu1.0005 Se1.053 0.21077187 -0.00005272 0.00014105 -0.00000001
ATVX 1 Mu1.0001 Se1.054 0.01992091 0.00000004 -0.00000001 -0.00000000
ATVX 1 Mu1.0002 Se1.054 0.13994094 -0.00016365 0.00035578 -0.00000006
ATVX 1 Mu1.0003 Se1.054 0.17863108 -0.00000112 0.00000259 -0.00000000
ATVX 1 Mu1.0004 Se1.054 0.19606236 0.00000118 -0.00000334 -0.00000000
ATVX 1 Mu1.0005 Se1.054 0.22406095 -0.00000051 0.00000136 -0.00000000
ATVX 1 Mu1.0001 Se1.055 0.01881755 0.00000000 -0.00000044 -0.00000000
ATVX 1 Mu1.0002 Se1.055 0.13883758 0.00000139 -0.00000309 -0.00000000
ATVX 1 Mu1.0003 Se1.055 0.17752772 0.00012001 -0.00027819 -0.00000003
ATVX 1 Mu1.0004 Se1.055 0.19495899 -0.00013483 0.00036688 -0.00000005
ATVX 1 Mu1.0005 Se1.055 0.22295759 0.00005623 -0.00014660 -0.00000001
ATVX 1 Mu1.0001 Se1.056 0.03510180 0.00000396 -0.00000163 -0.00000000
ATVX 1 Mu1.0002 Se1.056 0.15512183 0.00000030 -0.00000064 -0.00000000
ATVX 1 Mu1.0003 Se1.056 0.19381197 -0.00022297 0.00049681 -0.00000011
ATVX 1 Mu1.0004 Se1.056 0.21124324 0.00020478 -0.00058775 -0.00000012
ATVX 1 Mu1.0005 Se1.056 0.23924184 -0.00008937 0.00023401 -0.00000002
ATVX 1 Mu1.0001 Se1.057 0.03414420 -0.00000002 0.00000001 -0.00000000
ATVX 1 Mu1.0002 Se1.057 0.15416423 0.00029999 -0.00067334 -0.00000020
ATVX 1 Mu1.0003 Se1.057 0.19285437 0.00000097 -0.00000226 -0.00000000
ATVX 1 Mu1.0004 Se1.057 0.21028564 -0.00000115 0.00000316 -0.00000000
ATVX 1 Mu1.0005 Se1.057 0.23828424 0.00000049 -0.00000126 -0.00000000
ATVX 1 Mu1.0001 Se1.058 0.04628585 0.00002325 -0.00001517 -0.00000000
ATVX 1 Mu1.0002 Se1.058 0.16630589 -0.00000022 0.00000065 -0.00000000
ATVX 1 Mu1.0003 Se1.058 0.20499603 -0.00145490 0.00337725 -0.00000491
ATVX 1 Mu1.0004 Se1.058 0.22242730 0.00117908 -0.00329567 -0.00000389
ATVX 1 Mu1.0005 Se1.058 0.25042590 -0.00053464 0.00137484 -0.00000074
ATVX 1 Mu1.0001 Se1.059 0.06522755 0.00000008 -0.00000006 -0.00000000
ATVX 1 Mu1.0002 Se1.059 0.18524758 0.00019481 -0.00046246 -0.00000009
ATVX 1 Mu1.0003 Se1.059 0.22393772 -0.00000596 0.00001369 -0.00000000
ATVX 1 Mu1.0004 Se1.059 0.24136899 0.00000494 -0.00001363 -0.00000000
ATVX 1 Mu1.0005 Se1.059 0.26936759 -0.00000225 0.00000569 -0.00000000
ATVX 1 Mu1.0001 Se1.060 0.09341827 -0.00000179 0.00000032 -0.00000000
ATVX 1 Mu1.0002 Se1.060 0.21343830 -0.00000002 0.00000000 -0.00000000
ATVX 1 Mu1.0003 Se1.060 0.25212844 0.00027875 -0.00064759 -0.00000018
ATVX 1 Mu1.0004 Se1.060 0.26955971 -0.00023037 0.00060535 -0.00000014
ATVX 1 Mu1.0005 Se1.060 0.29755831 0.00010256 -0.00024875 -0.00000003
ATVX 1 Mu1.0001 Se1.061 0.10421887 0.00000002 -0.00000005 -0.00000000
ATVX 1 Mu1.0002 Se1.061 0.22423891 -0.00028217 0.00064495 -0.00000018
ATVX 1 Mu1.0003 Se1.061 0.26292905 0.00000006 0.00000000 0.00000000
ATVX 1 Mu1.0004 Se1.061 0.28036032 -0.00000037 0.00000102 -0.00000000
ATVX 1 Mu1.0001 Se1.062 0.13386501 -0.00000004 0.00000007 -0.00000000
ATVX 1 Mu1.0002 Se1.062 0.25388505 0.00063377 -0.00138826 -0.00000088
ATVX 1 Mu1.0003 Se1.062 0.29257519 -0.00000019 0.00000043 -0.00000000
ATVX 1 Mu1.0001 Se1.063 0.14856654 0.00000656 -0.00001171 -0.00000000
ATVX 1 Mu1.0002 Se1.063 0.26858657 0.00001149 -0.00002496 -0.00000000
ATVX 1 Mu1.0001 Se1.064 0.14785538 -0.00000016 0.00000027 -0.00000000
ATVX 1 Mu1.0002 Se1.064 0.26787541 0.00080116 -0.00173625 -0.00000139
ATVX 1 Mu1.0001 Se1.065 0.15992770 -0.00000002 0.00000004 -0.00000000
ATVX 1 Mu1.0002 Se1.065 0.27994773 -0.00049929 0.00109294 -0.00000055
ATVX 1 Mu1.0001 Se1.066 0.17752519 0.00000001 -0.00000001 -0.00000000
ATVX 1 Mu1.0002 Se1.066 0.29754522 0.00010442 -0.00024221 -0.00000003
ATVX 1 Mu1.0001 Se1.067 0.17247161 -0.00000081 -0.00000354 0.00000000
ATVX 1 Mu1.0002 Se1.067 0.29249164 0.00000012 -0.00000029 -0.00000000
ATVX 1 Mu1.0001 Se1.068 0.19099664 -0.00000002 0.00000005 -0.00000000
ATVX 1 Mu1.0001 Se1.069 0.20117035 -0.00000005 0.00000011 -0.00000000
ATVX 1 Mu1.0001 Se1.070 0.21447881 -0.00000381 0.00001910 -0.00000000
ATVX 1 Mu1.0001 Se1.071 0.21887158 0.00000003 -0.00000003 -0.00000000
ATVX 1 Mu1.0001 Se1.072 0.23912383 -0.00000005 0.00000009 -0.00000000
ATVX 1 Mu1.0001 Se1.073 0.25217848 -0.00000142 0.00000389 -0.00000000
ATVX 1 Mu1.0001 Se1.074 0.26156789 -0.00000004 0.00000008 -0.00000000
ATVX 1 Mu1.0001 Se1.075 0.25918933 -0.00000540 0.00002859 -0.00000000
ATVX 1 Mu1.0001 Se1.076 0.28058799 -0.00000005 0.00000012 -0.00000000
ATVX 1 Mu1.0001 Se1.077 0.27599979 0.00000423 -0.00001656 -0.00000000
ATVX 1 Mu1.0001 Se1.078 0.27712290 -0.00000011 0.00000040 -0.00000000
ATVX 1 Mu1.0001 Se1.079 0.29388865 0.00000007 -0.00000012 -0.00000000
ATVX 1 Mu1.0001 Se1.080 0.29102089 -0.00000389 0.00001082 -0.00000000
AIVX 1 Mu1.0001 In1.029 Se1.038 0.29069569 0.00000002 -0.00000004 -0.00000000
AIVX 1 Mu1.0001 In1.030 Se1.038 0.27958505 -0.00004187 0.00009563 -0.00000000
AIVX 1 Mu1.0001 In1.031 Se1.038 0.27370096 0.00000019 -0.00000042 -0.00000000
AIVX 1 Mu1.0001 In1.031 Se1.039 0.29558914 0.00000046 -0.00000103 -0.00000000
AIVX 1 Mu1.0063 In1.025 Se1.098 2.04177772 -0.05548984 0.02668600 -0.00148080
BJAIP 1 Se1.444 In1.004 Se1.444 In1.004 97.63798489 0.88667113 -0.00908117 -0.00805201
BJAIP 1 Se1.443 In1.009 Se1.443 In1.009 72.20756533 0.67001352 -0.00927892 -0.00621700
--Last edited by ABQTrap (2023-11-12 07:12:22)
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#2 2023-11-13 09:29:02
- Ignacio
- Administrator
- From: Uppsala
- Registered: 2015-11-03
- Posts: 1,011
Re: Is it OK if denominators of CASPT2 had small negative values?
Negative denominators are not necessarily a problem, but close-to-zero denominators may be. By using an imaginary shift you're already protecting yourself against small denominators. See https://pubs.acs.org/doi/10.1021/acs.jctc.2c00368
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#3 2023-11-13 10:27:06
- ABQTrap
- Member
- Registered: 2023-03-19
- Posts: 21
Re: Is it OK if denominators of CASPT2 had small negative values?
Dear Ignacio, Thank you for your reply. I did relaxed surface scan along the bond length, but there were three points of bond length that were hard to converge, should I increase the imaginary shift to improve the opimization convergence? Or any otheralternative ways?
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#4 2023-11-13 10:45:43
- Ignacio
- Administrator
- From: Uppsala
- Registered: 2015-11-03
- Posts: 1,011
Re: Is it OK if denominators of CASPT2 had small negative values?
That's hard to tell. What is it that doesn't converge, the energy (CASPT2) or the geometry optimization (SLAPAF)? Do you use numerical or analytical gradients? Do you use a multistate variant, which one? You could try the regularized version (but you'd probably have to redo all energies, and use numerical gradients). Perhaps the active space or the state averaging is not appropriate at those geometries.
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#5 2023-11-13 13:01:36
- ABQTrap
- Member
- Registered: 2023-03-19
- Posts: 21
Re: Is it OK if denominators of CASPT2 had small negative values?
Ignacio wrote:
That's hard to tell. What is it that doesn't converge, the energy (CASPT2) or the geometry optimization (SLAPAF)? Do you use numerical or analytical gradients? Do you use a multistate variant, which one? You could try the regularized version (but you'd probably have to redo all energies, and use numerical gradients). Perhaps the active space or the state averaging is not appropriate at those geometries.
Dear Ignacio, it was the issue of geometric optimization of CASPT2 using Gaussian's convergence criteria, sometimes the RMS and Max Displacements were difficult to converge, while the RMS and Max of gradients normally converged quickly. I used the analytical gradient, IPEA was set to zero. RASSCF calculated five states, but only ground state was chonsen for geometric optimization. Below is the input file, if there is something inappropriate, please let me know. Thanks a lot.
>>> FOREACH D in (1.8000)
&GATEWAY
coord=/home/qjq/openmolcas/singlet-1-3-1.8.xyz.
basis=DEF2-TZVPP
Constraints
d = Bond N2 N7
Values
d = $D Angstrom
End of Constraints
>>> COPY $MOLCAS/singlet-1-3-1.8.RasOrb INPORB
>>> Do While
&SEWARD
&SCF
charge=+1
zspin=0
&RASSCF
LUMOrb
nactel = 8 0 0
inactive= 31
ras2 = 6
spin = 1
ciroot = 5 5 1
rlxroot = 1
&CASPT2
frozen = 0
rlxroot = 1
MAXIter = 100
imaginary = 0.2
&MCLR
&ALASKA
&SLAPAF
MAXStep = 0.1
>>> EndDo
>>> END FOREACHLast edited by ABQTrap (2023-11-13 13:12:25)
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#6 2023-11-13 17:47:29
- Ignacio
- Administrator
- From: Uppsala
- Registered: 2015-11-03
- Posts: 1,011
Re: Is it OK if denominators of CASPT2 had small negative values?
You may want to use a multistate variant, especially if the ground state is crossing with S1.
As for the geometry optimization, you could add an energy criterion (e.g. "Thrs = 1.0e-6 3.0e-4" in SLAPAF) or try the RVO method ("Kriging" keyword), it may behave differently.
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