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You can choose an avatar and change the default style by going to "Profile" → "Personality" or "Display".#1 2025-09-18 13:32:25
- matlic
- Member
- Registered: 2023-06-22
- Posts: 5
CASSCF convergence problems with highly charged molecules
Hello everyone,
I am currently performing some CASSCF calculations on big molecular fragments with a negative charge of -11. However, I am experimenting problems in reaching convergence, since the energy is still fluctuating a lot (I report here the 16th iteration of the calculation):
++ --------- Input file ---------
&RASSCF
FILEORB = $WorkDir/$Project.RasOrb
THRS= 1.0e-06 1.0e+00 1.0e-3
Spin = 6
Nactel = 9 0 0
Ras2 = 7
Charge = -11
maxorb = 7
CiRoot = 21 21 1
ORBA = COMP
>>> COPY $WorkDir/$Project.RasOrb $CurrDir/Dy3_exp_sextconv.RasOrb
>>> COPY $WorkDir/$Project.JobIph $WorkDir/JOB001
-- ----------------------------------
--- Start Module: rasscf at Wed Sep 17 11:01:55 2025 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
&RASSCF
only a single process is used
available to each process: 38 GB of memory, 8 threads
pid: 23150
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
Header of the ONEINT file:
--------------------------
Integrals generated by Gateway/Seward, Thu Jul 17 18:38:22 2025
OrdInt status: non-squared
Cartesian coordinates in Angstrom:
-----------------------------------------------------
No. Label X Y Z
-----------------------------------------------------
1 DY 11.17770000 11.79760000 5.89180000
2 LU1 11.33040000 15.21180000 3.83240000
3 LU2 13.06180000 12.00140000 2.49170000
4 LU3 11.12870000 8.41060000 7.97690000
5 LU4 12.80440000 11.32600000 9.34820000
6 LU5 9.28840000 11.44860000 9.28200000
7 LU6 14.22810000 13.99840000 5.42530000
8 CL1 15.47840000 9.75770000 6.02080000
9 CL2 11.55410000 15.56660000 8.75270000
10 CL3 11.68790000 8.51020000 12.56480000
11 CL4 15.34460000 16.81410000 2.20860000
12 CL5 10.72790000 16.33220000 13.83980000
13 CL6 16.30460000 8.99210000 0.93370000
14 O1 11.10400000 12.77650000 3.69480000
15 O2 10.81530000 9.96370000 4.43200000
16 O3 13.29410000 11.88620000 4.91070000
17 O4 11.90650000 14.04930000 5.86360000
18 O5 8.91640000 12.57610000 5.63460000
19 O6 11.10110000 12.46550000 8.08550000
20 O7 9.84280000 10.27210000 7.23460000
21 O8 12.47390000 10.29910000 7.24200000
22 O9 10.73710000 14.72780000 1.61030000
23 O10 11.82610000 12.98840000 0.72980000
24 O11 8.98300000 14.64980000 3.96370000
25 O12 10.80640000 16.77530000 5.44400000
26 O13 12.36870000 16.90420000 2.45240000
27 O14 13.36920000 14.19610000 3.23100000
28 O15 13.35210000 10.49120000 0.54220000
29 O16 14.51870000 10.11260000 3.07290000
30 O17 11.34150000 10.33050000 2.31060000
31 O18 7.86930000 12.33200000 7.61130000
32 O19 10.21250000 7.86350000 5.86060000
33 O20 13.14690000 7.52890000 7.38820000
34 O21 11.43030000 6.99780000 9.92780000
35 O22 13.69560000 9.09140000 9.65000000
36 O23 10.97000000 9.92210000 9.72690000
37 O24 8.92320000 7.84250000 8.56570000
38 O25 7.80410000 9.64750000 9.28370000
39 O26 11.11760000 12.49290000 10.66790000
40 O27 8.33870000 13.46230000 10.03710000
41 O28 8.98270000 11.18010000 11.52180000
42 O29 13.66330000 11.12820000 11.54250000
43 O30 13.73840000 13.43810000 9.86280000
44 O31 15.12600000 11.27510000 8.90990000
45 O32 15.93140000 12.85880000 6.68800000
46 O33 14.55860000 15.02530000 7.53150000
47 O34 13.33690000 16.23290000 5.12340000
48 O35 16.06250000 15.40220000 5.04660000
49 O36 15.91490000 12.83140000 4.10550000
50 O37 14.97720000 12.74700000 1.39310000
51 N1 9.61570000 17.12040000 2.98420000
52 N2 10.95070000 5.84340000 7.44730000
53 C1 10.95250000 13.89750000 0.71500000
54 C2 7.85960000 15.44380000 3.51460000
55 C3 8.36450000 16.44900000 2.52180000
56 C4 9.54740000 17.42310000 5.44850000
57 C5 9.34790000 18.09220000 4.06710000
58 C6 10.24100000 17.79490000 1.81420000
59 C7 11.70860000 18.14740000 2.09780000
60 C8 10.65560000 9.78960000 3.21320000
61 C9 9.55780000 8.86470000 2.80990000
62 C10 8.32910000 9.03050000 3.48510000
63 C11 7.24440000 8.23150000 3.12610000
64 C12 7.40640000 7.29870000 2.09190000
65 C13 8.56860000 7.12460000 1.50250000
66 C14 9.69090000 7.88750000 1.81120000
67 C15 11.01880000 7.55820000 1.17600000
68 C16 11.05020000 7.32620000 -0.20980000
69 C17 12.28950000 6.99630000 -0.75490000
70 C18 13.40840000 6.84880000 -0.01180000
71 C19 13.36220000 7.07560000 1.33550000
72 C20 12.17020000 7.41740000 1.96040000
73 C21 9.83930000 5.63110000 6.50480000
74 C22 9.97950000 6.53940000 5.32440000
75 C23 12.24140000 5.36940000 6.86080000
76 C24 13.09260000 6.55130000 6.37480000
77 C25 10.65080000 5.11570000 8.70600000
78 C26 11.56240000 5.61400000 9.83620000
79 C27 7.91380000 12.62540000 6.39990000
80 C28 6.60770000 13.06160000 5.74100000
81 C29 6.24410000 12.50380000 4.55320000
82 C30 5.02100000 12.80820000 3.94010000
83 C31 4.18710000 13.64520000 4.57090000
84 C32 4.52640000 14.25350000 5.79860000
85 C33 5.76190000 14.00140000 6.38810000
86 C34 6.15770000 14.78940000 7.55520000
87 C35 7.37710000 15.40160000 7.62310000
88 C36 7.77940000 16.25080000 8.66460000
89 C37 6.88350000 16.38570000 9.72540000
90 C38 5.66920000 15.76380000 9.75790000
91 C39 5.25080000 14.97410000 8.62620000
92 C40 7.88530000 8.46760000 8.84190000
93 C41 8.07310000 10.58230000 12.46000000
94 C42 15.19860000 12.89720000 0.00150000
95 H1 7.44220000 15.90720000 4.28430000
96 H2 7.17980000 14.86120000 3.09360000
97 H3 7.66460000 17.13250000 2.36820000
98 H4 8.53680000 15.99360000 1.65910000
99 H5 9.52010000 18.10570000 6.16500000
100 H6 8.82740000 16.76590000 5.61540000
101 H7 8.41930000 18.42670000 3.99180000
102 H8 9.96170000 18.86470000 3.98000000
103 H9 9.73910000 18.62220000 1.60290000
104 H10 10.19350000 17.19870000 1.02530000
105 H11 12.12980000 18.54660000 1.29560000
106 H12 11.76840000 18.79610000 2.84240000
107 H13 8.24140000 9.67820000 4.17500000
108 H14 6.41240000 8.31760000 3.57370000
109 H15 6.66100000 6.78180000 1.81120000
110 H16 8.64700000 6.44940000 0.83910000
111 H17 10.26950000 7.38770000 -0.74610000
112 H18 12.35220000 6.87110000 -1.69450000
113 H19 14.22270000 6.58630000 -0.42400000
114 H20 14.15600000 6.99820000 1.85110000
115 H21 12.13670000 7.55330000 2.90000000
116 H22 8.97860000 5.80910000 6.96130000
117 H23 9.83760000 4.68860000 6.20040000
118 H24 10.74160000 6.25780000 4.75850000
119 H25 9.15510000 6.52790000 4.77770000
120 H26 12.05320000 4.76430000 6.10000000
121 H27 12.74570000 4.85960000 7.54330000
122 H28 14.00730000 6.23870000 6.15910000
123 H29 12.69620000 6.93800000 5.55480000
124 H30 10.79130000 4.14450000 8.57010000
125 H31 9.70310000 5.25940000 8.95420000
126 H32 11.30150000 5.19250000 10.69300000
127 H33 12.50280000 5.37570000 9.64410000
128 H34 6.83650000 11.89290000 4.12920000
129 H35 4.78980000 12.43000000 3.09950000
130 H36 3.34250000 13.83440000 4.18090000
131 H37 3.90990000 14.83660000 6.22410000
132 H38 7.99320000 15.24220000 6.91840000
133 H39 8.61340000 16.70520000 8.64990000
134 H40 7.12930000 16.93640000 10.45960000
135 H41 5.10790000 15.85180000 10.51870000
136 H42 4.38350000 14.58440000 8.59960000
137 H43 7.81780000 9.68090000 12.14530000
138 H44 7.25260000 11.13300000 12.51900000
139 H45 10.68500000 12.15160000 3.25020000
140 H46 11.68380000 14.82120000 6.26400000
141 H47 13.90320000 14.75470000 2.79220000
142 H48 14.01470000 11.38180000 5.03780000
143 H49 11.24280000 13.34460000 8.16970000
144 H50 9.01800000 10.21440000 6.89920000
145 H51 10.68700000 9.67500000 10.53350000
146 H52 13.14060000 9.78040000 6.94350000
147 H53 11.11820000 13.36910000 10.50390000
148 H54 13.18350000 8.61100000 10.19370000
149 H55 10.56310000 7.19870000 10.04600000
150 H56 10.40530000 8.59390000 5.37750000
151 H57 8.78830000 14.03840000 4.57980000
152 H58 13.14670000 16.93300000 2.02400000
153 H59 15.44460000 12.02310000 -0.39300000
154 H60 14.37050000 13.21150000 -0.43730000
155 H61 15.34870000 10.50320000 8.50950000
156 H62 13.12930000 10.56960000 11.98130000
157 H63 13.01780000 13.94250000 9.73570000
158 H64 15.78970000 11.97980000 6.60370000
159 H65 16.34550000 15.64940000 4.24000000
160 H66 13.89190000 15.54400000 7.82990000
161 H67 15.91430000 11.95520000 4.26950000
162 H68 13.84900000 16.71330000 4.57980000
163 H69 14.32790000 10.34850000 0.46640000
164 H70 13.10310000 11.03160000 -0.24890000
165 H71 15.31240000 10.47690000 3.54010000
166 H72 14.00840000 9.58610000 3.73700000
167 H73 8.59660000 13.52010000 10.99130000
168 H74 8.86420000 14.17360000 9.59220000
169 H75 8.55990000 10.50130000 13.45340000
170 H76 16.00300000 13.64170000 -0.16890000
171 H77 7.37759400 7.85422000 9.58481400
172 H78 11.17447100 14.48892300 -0.17205600
-----------------------------------------------------
Nuclear repulsion energy =69369.89381323
++ Wave function specifications:
-----------------------------
Number of closed shell electrons 1236
Number of electrons in active shells 9
Max number of holes in RAS1 space 0
Max nr of electrons in RAS3 space 0
Number of inactive orbitals 618
Number of active orbitals 7
Number of secondary orbitals 566
Spin quantum number 2.5
State symmetry 1
--
++ Orbital specifications:
-----------------------
Symmetry species 1
a
Frozen orbitals 0
Inactive orbitals 618
Active orbitals 7
RAS1 orbitals 0
RAS2 orbitals 7
RAS3 orbitals 0
Secondary orbitals 566
Deleted orbitals 0
Number of basis functions 1191
--
++ CI expansion specifications:
----------------------------
Number of CSFs 21
Number of determinants 21
Number of root(s) required 21
Root chosen for geometry opt. 21
CI roots used 1 2 3 4 5 6 7 8 9 10
11 12 13 14 15 16 17 18 19 20
21
weights 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048
0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048
0.048
highest root included in the CI 21
max. size of the explicit Hamiltonian 21
--
++ Optimization specifications:
----------------------------
RASSCF algorithm: LK Cholesky
Maximum number of macro iterations 200
Maximum number of SX iterations 100
Threshold for RASSCF energy 0.100E-05
Threshold for max MO rotation 0.100E+01
Threshold for max BLB element 0.100E-02
Level shift parameter 0.500E+00
Make Quasi-Newton update
--
The MO-coefficients are taken from the file:
/g100_work/IscrC_Halo-SMT/Cu4Dy12_allCl/Dy3_exp/Dy3_exp.RasOrb
Title: RASSCF average (pseudo-natural) orbitals (Not final)
Total molecular charge -11.00
************************************************************************************************************************
* *
* Wave function control section *
* *
************************************************************************************************************************
RASSCF iterations: Energy and convergence statistics
----------------------------------------------------
Iter CI SX CI RASSCF Energy max ROT max BLB max BLB Level Ln srch Step QN Walltime
iter iter root energy change param element value shift minimum type update hh:mm:ss
Nr of preliminary CI iterations: 1
Total energies have been shifted. Add -106000.00 au
1 1 12 0 -721.93678503 0.00E+00 -0.86E-02 2721134 1 0.38E-01* 0.52 0.00 SX NO 8:48:22
2 1 13 0 -721.93880520 -0.20E-02* -0.98E-02 2721134 1 -0.35E-01* 0.47 0.00 SX NO 2:11:47
3 1 12 0 -721.94076119 -0.20E-02* -0.86E-02 2721134 1 0.32E-01* 0.52 0.00 SX NO 2:11:00
4 1 12 0 -721.94247019 -0.17E-02* -0.91E-02 2721134 1 -0.30E-01* 0.47 0.00 SX NO 2:09:31
5 1 12 0 -721.94410289 -0.16E-02* 0.11E-01 2721134 1 0.28E-01* 0.52 0.81 QN YES 2:10:35
6 1 12 0 -721.94622907 -0.21E-02* 0.65E-01 2721134 1 0.16E-01* 0.51 2.50 QN YES 2:10:05
7 1 12 0 -721.95362565 -0.74E-02* -0.29E-01 2721134 1 -0.11E-01* 0.48 1.31 QN YES 2:16:02What can I do to make the calculation going faster and smoother?
Thank you in advance!
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