SCF does not converge in charged system
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Sun Geng
Sep 16, 2020, 6:15:08 PM9/16/20
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Dear CP2K users,
Best Regards,
Geng
I am using CP2K to study a bulk system with +1 charge, and try to optimize the structure.
here is the input:
&FORCE_EVAL
&DFT
CHARGE 1
UKS
BASIS_SET_FILE_NAME BASIS_MOLOPT_UCL
BASIS_SET_FILE_NAME BASIS_MOLOPT
BASIS_SET_FILE_NAME BASIS_ADMM_MOLOPT
BASIS_SET_FILE_NAME BASIS_ADMM
POTENTIAL_FILE_NAME GTH_POTENTIALS
&MGRID
CUTOFF 550
REL_CUTOFF 50
COMMENSURATE
&END MGRID
&QS
EXTRAPOLATION PS
EXTRAPOLATION_ORDER 3
EPS_DEFAULT 1.0E-12
MAP_CONSISTENT T
&END QS
&SCF
SCF_GUESS RESTART
EPS_SCF 1.0E-7
MAX_SCF 300
ADDED_MOS 100 100
&DIAGONALIZATION
ALGORITHM STANDARD
&END DIAGONALIZATION
&SMEAR ON
METHOD FERMI_DIRAC
ELECTRONIC_TEMPERATURE [K] 300
&END SMEAR
&MIXING
METHOD BROYDEN_MIXING
ALPHA 0.2
BETA 1.5
NBROYDEN 8
&END MIXING
&END SCF
&XC
&XC_FUNCTIONAL PBE
&END XC_FUNCTIONAL
&END XC
&END DFT
&SUBSYS
&KIND H
BASIS_SET DZVP-MOLOPT-SR-GTH-q1
POTENTIAL GTH-PBE-q1
&END KIND
&KIND O
BASIS_SET DZVP-MOLOPT-SR-GTH-q6
POTENTIAL GTH-PBE-q6
&END KIND
&KIND W
BASIS_SET DZVP-MOLOPT-SR-GTH-q14
POTENTIAL GTH-PBE-q14
&END KIND
&KIND P
BASIS_SET DZVP-MOLOPT-SR-GTH-q5
POTENTIAL GTH-PBE-q5
&END KIND
&KIND Ag
BASIS_SET DZVP-MOLOPT-SR-GTH-q11
POTENTIAL GTH-PBE-q11
&END KIND
&CELL
PERIODIC XYZ
CELL_FILE_FORMAT CIF
CELL_FILE_NAME optimized.cif
&END CELL
&TOPOLOGY
COORD_FILE_FORMAT CIF
COORD_FILE_NAME optimized.cif
&END
&END SUBSYS
&END FORCE_EVAL
and here is the output for SCF part:
Spin 1
Number of electrons: 446
Number of occupied orbitals: 446
Number of molecular orbitals: 546
Spin 2
Number of electrons: 445
Number of occupied orbitals: 445
Number of molecular orbitals: 545
Number of orbital functions: 1840
Number of independent orbital functions: 1840
Extrapolation method: initial_guess
*** WARNING in qs_initial_guess.F:280 :: User requested to restart the ***
*** wavefunction from the file named: cp2k-RESTART.wfn. This file does ***
*** not exist. Please check the existence of the file or change properly ***
*** the value of the keyword WFN_RESTART_FILE_NAME. Calculation continues ***
*** using ATOMIC GUESS. ***
SCF WAVEFUNCTION OPTIMIZATION
Step Update method Time Convergence Total energy Change
------------------------------------------------------------------------------
1 NoMix/Diag. 0.20E+00 29.2 0.89451076 -3162.6429026815 -3.16E+03
2 Broy./Diag. 0.20E+00 42.7 0.06835387 -3049.3301192902 1.13E+02
3 Broy./Diag. 0.20E+00 40.9 0.13673666 -3118.6830929147 -6.94E+01
4 Broy./Diag. 0.20E+00 35.7 0.06958362 -3172.9617597277 -5.43E+01
5 Broy./Diag. 0.20E+00 45.9 0.09834453 -3156.7580584199 1.62E+01
6 Broy./Diag. 0.20E+00 40.6 0.08099131 -3158.2583063423 -1.50E+00
7 Broy./Diag. 0.20E+00 32.1 0.03272365 -3157.4381248235 8.20E-01
8 Broy./Diag. 0.20E+00 36.5 0.01783385 -3156.7305115815 7.08E-01
9 Broy./Diag. 0.20E+00 34.8 0.02118559 -3157.7282159160 -9.98E-01
10 Broy./Diag. 0.20E+00 32.2 0.01011534 -3158.9127284866 -1.18E+00
11 Broy./Diag. 0.20E+00 41.7 0.01396047 -3159.1191669326 -2.06E-01
12 Broy./Diag. 0.20E+00 30.5 0.02559684 -3159.1783839356 -5.92E-02
13 Broy./Diag. 0.20E+00 32.8 0.00532253 -3159.2177559710 -3.94E-02
14 Broy./Diag. 0.20E+00 31.8 0.02180308 -3159.1717434947 4.60E-02
15 Broy./Diag. 0.20E+00 36.2 0.01648805 -3159.1430712622 2.87E-02
16 Broy./Diag. 0.20E+00 26.4 0.03447719 -3158.9593624648 1.84E-01
17 Broy./Diag. 0.20E+00 34.5 0.01780160 -3158.8442985597 1.15E-01
18 Broy./Diag. 0.20E+00 26.8 0.01657931 -3158.8923825923 -4.81E-02
19 Broy./Diag. 0.20E+00 34.8 0.02037717 -3158.8916640827 7.19E-04
20 Broy./Diag. 0.20E+00 42.5 0.00485428 -3158.8961038765 -4.44E-03
21 Broy./Diag. 0.20E+00 39.6 0.01150238 -3158.8792816504 1.68E-02
22 Broy./Diag. 0.20E+00 31.7 0.00418097 -3158.8345904231 4.47E-02
23 Broy./Diag. 0.20E+00 42.6 0.00868663 -3158.8200898050 1.45E-02
24 Broy./Diag. 0.20E+00 28.0 0.02012795 -3158.8361601235 -1.61E-02
25 Broy./Diag. 0.20E+00 41.8 0.00273285 -3158.8696842529 -3.35E-02
26 Broy./Diag. 0.20E+00 38.0 0.01834681 -3158.9169936183 -4.73E-02
27 Broy./Diag. 0.20E+00 25.4 0.00390719 -3158.9254900262 -8.50E-03
28 Broy./Diag. 0.20E+00 36.7 0.00732661 -3158.9313554692 -5.87E-03
29 Broy./Diag. 0.20E+00 28.4 0.00944093 -3158.9309376819 4.18E-04
30 Broy./Diag. 0.20E+00 36.5 0.00575205 -3158.9309675431 -2.99E-05
31 Broy./Diag. 0.20E+00 24.2 0.00694190 -3158.9348626028 -3.90E-03
32 Broy./Diag. 0.20E+00 31.6 0.00379752 -3158.9366629862 -1.80E-03
33 Broy./Diag. 0.20E+00 22.5 0.00774378 -3158.9435293508 -6.87E-03
34 Broy./Diag. 0.20E+00 24.8 0.00951415 -3158.9464593354 -2.93E-03
35 Broy./Diag. 0.20E+00 42.1 0.00751249 -3158.9376966328 8.76E-03
36 Broy./Diag. 0.20E+00 26.2 0.00199334 -3158.9353993219 2.30E-03
37 Broy./Diag. 0.20E+00 34.9 0.00427585 -3158.9336122741 1.79E-03
38 Broy./Diag. 0.20E+00 23.0 0.00193232 -3158.9300421729 3.57E-03
39 Broy./Diag. 0.20E+00 36.9 0.00141459 -3158.9253000238 4.74E-03
40 Broy./Diag. 0.20E+00 28.7 0.00308787 -3158.9259688644 -6.69E-04
41 Broy./Diag. 0.20E+00 37.6 0.00099441 -3158.9283356817 -2.37E-03
42 Broy./Diag. 0.20E+00 37.7 0.00086304 -3158.9295288981 -1.19E-03
43 Broy./Diag. 0.20E+00 31.0 0.00233147 -3158.9321116185 -2.58E-03
44 Broy./Diag. 0.20E+00 38.8 0.00282812 -3158.9332794477 -1.17E-03
45 Broy./Diag. 0.20E+00 32.3 0.00179904 -3158.9355324522 -2.25E-03
46 Broy./Diag. 0.20E+00 38.4 0.00070900 -3158.9356072233 -7.48E-05
47 Broy./Diag. 0.20E+00 26.3 0.00178940 -3158.9359573955 -3.50E-04
48 Broy./Diag. 0.20E+00 22.5 0.00148086 -3158.9358158944 1.42E-04
49 Broy./Diag. 0.20E+00 22.6 0.00133155 -3158.9361011237 -2.85E-04
50 Broy./Diag. 0.20E+00 22.4 0.00108193 -3158.9353836539 7.17E-04
51 Broy./Diag. 0.20E+00 22.5 0.00475385 -3158.9365929745 -1.21E-03
52 Broy./Diag. 0.20E+00 22.5 0.00101417 -3158.9414298715 -4.84E-03
53 Broy./Diag. 0.20E+00 22.5 0.00074742 -3158.9408986224 5.31E-04
54 Broy./Diag. 0.20E+00 37.2 0.00160292 -3158.9399250202 9.74E-04
55 Broy./Diag. 0.20E+00 35.0 0.00180981 -3158.9389882830 9.37E-04
56 Broy./Diag. 0.20E+00 34.1 0.00101710 -3158.9389977636 -9.48E-06
57 Broy./Diag. 0.20E+00 23.0 0.00114587 -3158.9392492436 -2.51E-04
58 Broy./Diag. 0.20E+00 37.8 0.00220519 -3158.9387605750 4.89E-04
59 Broy./Diag. 0.20E+00 30.4 0.00032853 -3158.9385569682 2.04E-04
60 Broy./Diag. 0.20E+00 29.3 0.00205265 -3158.9386583532 -1.01E-04
61 Broy./Diag. 0.20E+00 27.8 0.00139873 -3158.9383562600 3.02E-04
62 Broy./Diag. 0.20E+00 38.4 0.00024160 -3158.9390152530 -6.59E-04
63 Broy./Diag. 0.20E+00 28.3 0.00573947 -3158.9396907479 -6.75E-04
64 Broy./Diag. 0.20E+00 38.1 0.00196458 -3158.9410245046 -1.33E-03
65 Broy./Diag. 0.20E+00 45.2 0.00179614 -3158.9411543337 -1.30E-04
66 Broy./Diag. 0.20E+00 29.7 0.00452601 -3158.9414841380 -3.30E-04
67 Broy./Diag. 0.20E+00 35.4 0.00172292 -3158.9413898840 9.43E-05
68 Broy./Diag. 0.20E+00 37.1 0.00326630 -3158.9409273881 4.62E-04
69 Broy./Diag. 0.20E+00 45.2 0.00217994 -3158.9412881453 -3.61E-04
70 Broy./Diag. 0.20E+00 40.6 0.00177248 -3158.9411038537 1.84E-04
71 Broy./Diag. 0.20E+00 40.5 0.00556252 -3158.9403155792 7.88E-04
72 Broy./Diag. 0.20E+00 38.5 0.00065509 -3158.9381473872 2.17E-03
73 Broy./Diag. 0.20E+00 32.8 0.00070470 -3158.9382797518 -1.32E-04
74 Broy./Diag. 0.20E+00 44.3 0.00147190 -3158.9383945291 -1.15E-04
75 Broy./Diag. 0.20E+00 32.6 0.00209594 -3158.9378160701 5.78E-04
76 Broy./Diag. 0.20E+00 42.1 0.00063422 -3158.9378127379 3.33E-06
77 Broy./Diag. 0.20E+00 38.5 0.00354342 -3158.9377893967 2.33E-05
78 Broy./Diag. 0.20E+00 22.4 0.00249106 -3158.9395472286 -1.76E-03
79 Broy./Diag. 0.20E+00 41.5 0.00199009 -3158.9386306696 9.17E-04
80 Broy./Diag. 0.20E+00 44.9 0.00133807 -3158.9383378799 2.93E-04
81 Broy./Diag. 0.20E+00 44.5 0.00165782 -3158.9382333617 1.05E-04
82 Broy./Diag. 0.20E+00 32.9 0.00047526 -3158.9388671865 -6.34E-04
83 Broy./Diag. 0.20E+00 42.9 0.00048036 -3158.9385637254 3.03E-04
84 Broy./Diag. 0.20E+00 45.5 0.00107296 -3158.9386852294 -1.22E-04
85 Broy./Diag. 0.20E+00 41.7 0.00142251 -3158.9383795982 3.06E-04
86 Broy./Diag. 0.20E+00 42.1 0.00082982 -3158.9382992687 8.03E-05
87 Broy./Diag. 0.20E+00 32.3 0.00130730 -3158.9378720570 4.27E-04
88 Broy./Diag. 0.20E+00 43.4 0.00160192 -3158.9379381501 -6.61E-05
89 Broy./Diag. 0.20E+00 44.9 0.00200376 -3158.9369819375 9.56E-04
90 Broy./Diag. 0.20E+00 48.4 0.00030780 -3158.9372356839 -2.54E-04
91 Broy./Diag. 0.20E+00 39.3 0.00041707 -3158.9377762720 -5.41E-04
92 Broy./Diag. 0.20E+00 40.1 0.00058788 -3158.9372819846 4.94E-04
93 Broy./Diag. 0.20E+00 40.5 0.00136910 -3158.9371474170 1.35E-04
94 Broy./Diag. 0.20E+00 39.8 0.00016182 -3158.9367337407 4.14E-04
95 Broy./Diag. 0.20E+00 26.6 0.00238628 -3158.9369656511 -2.32E-04
96 Broy./Diag. 0.20E+00 43.7 0.00116006 -3158.9373876912 -4.22E-04
97 Broy./Diag. 0.20E+00 45.1 0.00207758 -3158.9368022064 5.85E-04
98 Broy./Diag. 0.20E+00 43.6 0.00079290 -3158.9364548934 3.47E-04
99 Broy./Diag. 0.20E+00 46.2 0.00092796 -3158.9372004011 -7.46E-04
100 Broy./Diag. 0.20E+00 38.2 0.00500334 -3158.9376972675 -4.97E-04
101 Broy./Diag. 0.20E+00 40.1 0.00106711 -3158.9381744626 -4.77E-04
102 Broy./Diag. 0.20E+00 41.7 0.00343650 -3158.9377555298 4.19E-04
103 Broy./Diag. 0.20E+00 44.8 0.00267783 -3158.9383934292 -6.38E-04
104 Broy./Diag. 0.20E+00 45.6 0.00071476 -3158.9375202197 8.73E-04
105 Broy./Diag. 0.20E+00 40.4 0.00155390 -3158.9378390866 -3.19E-04
106 Broy./Diag. 0.20E+00 38.8 0.00234517 -3158.9387128348 -8.74E-04
107 Broy./Diag. 0.20E+00 48.5 0.00097231 -3158.9396178203 -9.05E-04
108 Broy./Diag. 0.20E+00 38.3 0.00080812 -3158.9398610567 -2.43E-04
109 Broy./Diag. 0.20E+00 34.3 0.00215088 -3158.9389043870 9.57E-04
110 Broy./Diag. 0.20E+00 31.4 0.00177769 -3158.9383907222 5.14E-04
111 Broy./Diag. 0.20E+00 44.8 0.00065825 -3158.9381760277 2.15E-04
112 Broy./Diag. 0.20E+00 45.5 0.00215273 -3158.9383009723 -1.25E-04
113 Broy./Diag. 0.20E+00 41.6 0.00109198 -3158.9393934584 -1.09E-03
114 Broy./Diag. 0.20E+00 40.0 0.00093046 -3158.9396303494 -2.37E-04
115 Broy./Diag. 0.20E+00 43.3 0.00176033 -3158.9399720471 -3.42E-04
116 Broy./Diag. 0.20E+00 40.1 0.00096409 -3158.9397376651 2.34E-04
117 Broy./Diag. 0.20E+00 45.3 0.00125691 -3158.9392869885 4.51E-04
118 Broy./Diag. 0.20E+00 44.2 0.00132855 -3158.9387103155 5.77E-04
119 Broy./Diag. 0.20E+00 42.3 0.00149879 -3158.9386595393 5.08E-05
120 Broy./Diag. 0.20E+00 30.4 0.00143229 -3158.9384132380 2.46E-04
121 Broy./Diag. 0.20E+00 43.8 0.00179008 -3158.9380890800 3.24E-04
122 Broy./Diag. 0.20E+00 43.4 0.00099314 -3158.9380058169 8.33E-05
123 Broy./Diag. 0.20E+00 42.1 0.00091292 -3158.9385543943 -5.49E-04
124 Broy./Diag. 0.20E+00 34.8 0.00048706 -3158.9392044760 -6.50E-04
125 Broy./Diag. 0.20E+00 43.0 0.00207348 -3158.9394986504 -2.94E-04
126 Broy./Diag. 0.20E+00 45.9 0.00153626 -3158.9405092916 -1.01E-03
127 Broy./Diag. 0.20E+00 40.5 0.00316672 -3158.9406092849 -1.00E-04
128 Broy./Diag. 0.20E+00 43.6 0.00060328 -3158.9411260512 -5.17E-04
129 Broy./Diag. 0.20E+00 40.9 0.00124325 -3158.9398080085 1.32E-03
130 Broy./Diag. 0.20E+00 40.1 0.00105586 -3158.9390224278 7.86E-04
131 Broy./Diag. 0.20E+00 35.2 0.00376178 -3158.9392740528 -2.52E-04
132 Broy./Diag. 0.20E+00 42.1 0.00145841 -3158.9393697934 -9.57E-05
133 Broy./Diag. 0.20E+00 42.1 0.00071196 -3158.9393684613 1.33E-06
134 Broy./Diag. 0.20E+00 41.2 0.00179287 -3158.9391322902 2.36E-04
135 Broy./Diag. 0.20E+00 38.1 0.00044719 -3158.9392016770 -6.94E-05
136 Broy./Diag. 0.20E+00 41.2 0.00157808 -3158.9394541806 -2.53E-04
137 Broy./Diag. 0.20E+00 47.0 0.00098181 -3158.9396660200 -2.12E-04
138 Broy./Diag. 0.20E+00 39.5 0.00162220 -3158.9396913205 -2.53E-05
139 Broy./Diag. 0.20E+00 43.0 0.00289676 -3158.9400550759 -3.64E-04
140 Broy./Diag. 0.20E+00 39.7 0.00149967 -3158.9406717084 -6.17E-04
141 Broy./Diag. 0.20E+00 46.1 0.00159591 -3158.9412353749 -5.64E-04
142 Broy./Diag. 0.20E+00 42.4 0.00187668 -3158.9411012693 1.34E-04
143 Broy./Diag. 0.20E+00 40.1 0.00067059 -3158.9401622911 9.39E-04
144 Broy./Diag. 0.20E+00 38.5 0.00078557 -3158.9394849052 6.77E-04
145 Broy./Diag. 0.20E+00 41.4 0.00040215 -3158.9390501939 4.35E-04
146 Broy./Diag. 0.20E+00 44.3 0.00050394 -3158.9388948113 1.55E-04
147 Broy./Diag. 0.20E+00 40.1 0.00021931 -3158.9388883119 6.50E-06
148 Broy./Diag. 0.20E+00 37.5 0.00008719 -3158.9387984249 8.99E-05
149 Broy./Diag. 0.20E+00 39.7 0.00027253 -3158.9386912028 1.07E-04
150 Broy./Diag. 0.20E+00 49.0 0.00024084 -3158.9387118442 -2.06E-05
151 Broy./Diag. 0.20E+00 38.3 0.00056008 -3158.9386458855 6.60E-05
152 Broy./Diag. 0.20E+00 39.0 0.00023938 -3158.9386947094 -4.88E-05
153 Broy./Diag. 0.20E+00 34.3 0.00032498 -3158.9386747222 2.00E-05
154 Broy./Diag. 0.20E+00 42.4 0.00012525 -3158.9385975305 7.72E-05
155 Broy./Diag. 0.20E+00 33.1 0.00018100 -3158.9385321803 6.54E-05
156 Broy./Diag. 0.20E+00 39.9 0.00040027 -3158.9384314946 1.01E-04
157 Broy./Diag. 0.20E+00 43.0 0.00092647 -3158.9384077964 2.37E-05
The SCF did not converge in 157 steps and then I killed the job.
I also tried to increase the CUTOFF to 800 Ry, but it did not work.
Switching the SCF method to OT method also did not help.
Is there anything trick that improves the convergence?
Thank you very much in advance.
Best Regards,
Geng
HB H
Sep 16, 2020, 9:47:52 PM9/16/20
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Hi there,
Maybe you should provide the intact and full input. For example, where is the &GLOBAL and &MOTION sections?
A quick advice is to use different optimizers such as "BFGS, CG or LBFGS".
Cheers,
Haibei
Sun Geng <gengs...@gmail.com> 于2020年9月17日周四 上午6:15写道：
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Sun Geng
Sep 16, 2020, 11:35:18 PM9/16/20
to cp2k
Hi Haibei,
Thank you for your reply, below is the &global and &motion inputs,
but I would think the SCF convergence is not related to those ionic movement setups.
I have not get the first SCF cycle converged yet.
Best,
Geng
Best,
Geng
&GLOBAL
PROJECT cp2k
PRINT_LEVEL LOW
! PREFERRED_FFT_LIBRARY FFTSG
PREFERRED_DIAG_LIBRARY ELPA
RUN_TYPE GEO_OPT
&END GLOBAL
&MOTION
&GEO_OPT
TYPE MINIMIZATION
MAX_ITER 200
OPTIMIZER CG
&END GEO_OPT
&PRINT
&TRAJECTORY
FILENAME structure_opt
&EACH
QS_SCF -1
GEO_OPT 1
&END
&END
&END
&END MOTION
HB H
Sep 17, 2020, 2:36:47 AM9/17/20
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Hi,
I am not an expert of CP2K, but I know you need to be carefull when metal atoms are involved (i.e. Ag atoms) in CP2K.
Normally the uncoverged result indicates a bad initial geometry, which means you need to double check the validity of your input structure.
Good luck!
Haibei
Sun Geng <gengs...@gmail.com> 于2020年9月17日周四 上午11:35写道：
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Krack Matthias (PSI)
Sep 17, 2020, 3:19:04 AM9/17/20
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Dear Geng
based on the limited information you provide about your system, one can only guess. I would try a larger electronic temperature for the smearing, e.g. 2000K instead of 300K.
HTH
Matthias
--
Anton S. Lytvynenko
Sep 18, 2020, 6:26:00 AM9/18/20
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Dear Sun,
1. 157 is not an immense number, and your system seems to move
toward convergence -- it is possible that you get your system
converged just by keeping the program working.
2. Is it your first optimization step? The next ones should converge better. Even if SCF is not fully converged in the 1st step, it still can produce reasonable structure for the 2nd step which should converge better (sometimes it is the only method if your initial geometry is intrinsically poor).
3. Your energy mostly oscillates within 10-4 -- 10-5 Eh changing dE from + to - and vice versa. I would consider reducing ALPHA.
4. You told nothing about the nature of your system. E.g. if it is metallic phase, you can benefit from Kerker mixing with, say, BETA 1.5.
Hope that helps.
Yours,
Anton
17.09.20 01:15, Sun Geng пише:
Sun Geng
Sep 19, 2020, 10:18:55 AM9/19/20
to cp2k
Dear Haibei,
Matthias and Anton,
Thank you very much for help.
Finally, Increasing the the smearing temperature from 300K to 1000K solved the problem.
The first SCF step converged in 45 steps, and continues smoothly.
My target system is a ionic crystalline with large band gap.
I will also give some tests using Anton's suggestions by decreasing alpha and will get you updated.
Best Regards,
Geng
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