[molpro-user] {SPAM}? convergence of conial optg
liuxj at iccas.ac.cn
liuxj at iccas.ac.cn
Tue Jul 5 05:28:34 BST 2005
Dear users
I optimized conical intersection of 2 states according to the manual.
Optimization repeatedly called opt inside a do-loop cycle. When the
variable OPTCONV was below 1*10-4, the threshold I predefined, opt was
done. But I found the energy difference of the 2 states is 1*10-2,which is
quite big. How can I define the threshold of the energy differrence of 2
states? What is variable OPTCONV, energy or gradient or something else?
attachment is the output
thank you in advance
best regards
liu xiaojun
-----------------------------------------------
-------------- next part --------------
MPP nodes nproc
hartree 1
ga_uses_ma=true, calling ma_init with heap size 8010000 determined by size of -G / nprocs
Primary working directories: /tmp/liuxj
Secondary working directories: /tmp/liuxj
blaslib=atlas
MPP tuning parameters: Latency= 1000 Microseconds, Broadcast speed= 20 MB/sec
default implementation of scratch files=df
***,
Including file /usr/local/lib/molpro-mpp-Linux-i686-i4-2002.6/molproi.rc
***,conical of singlet and triplet states of fn3
memory,346,m
file,2,75.wfu,new
basis={spd,f,vdz;spd,n,vdz}
geometry={x;
f
n 1 fn
n 2 n1n2 1 n2n1f
n 3 n2n3 2 n3n2n1 1 180.0}
FN = 1.37827976 ang
N1N2 = 1.75000000 ang
N2N3 = 1.10300517 ang
N2N1F = 102.87102741
N3N2N1 = 163.09844307
int
maxstep=50
do i=1,maxstep
if (i.eq.1) hf
multi;occ,15,4;closed,6;wf,30,1,0;state,1;wf,30,2,2;state,1
cpmcscf,grad,1.1,spin=0,accu=1.0d-7,record=5101.1
cpmcscf,grad,1.2,spin=1,accu=1.0d-7,record=5102.1
force;samc,5101.1;conical,6100.1,nodc
force;samc,5102.1;conical,6100.1,nodc
opt,gradient=1.d-5,step=1.d-4;inactive,n1n2
show,fn,n1n2,n2n3,n2n1f,n3n2n1,e
if(optconv.lt.1.d-4) exit
enddo
---
Variables initialized (303), CPU time= 0.00 sec
Default parameters read. Elapsed time= 0.00 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, University of Birmingham, 1997
Version 2002.6 linked 7 Nov 2003 10:22:41
**********************************************************************************************************************************
LABEL * CONICAL OF SINGLET AND TRIPLET STATES OF FN3
Linux-2.6.5-7.97-smp/hartree(x86_64) 32 bit mpp version DATE: 21-Jun-05 TIME: 20:19:14
**********************************************************************************************************************************
Installed patches: cidps_orthp configure_xeon darwin_conf dft_orbital_hi enest_dummy fujitsu-ssl2
fujitsu_conf ga_conflict2 ia64root_check merge_orbdom mkl60 modelopt
molden_orbital_normalization mpputil mxm_fujitsu nec_parse opteron2 patcher_printf
posinp pseudo_libmol2 readop_multipole_nps sun_forte8
**********************************************************************************************************************************
Variable memory set to 346000000 words, buffer space 230000 words
Permanent file 2 75.wfu assigned. Implementation=df
SETTING FN = 1.37827976 ANG
SETTING N1N2 = 1.75000000 ANG
SETTING N2N3 = 1.10300517 ANG
SETTING N2N1F = 102.87102741
SETTING N3N2N1 = 163.09844307
Using spherical harmonics
Library entry F S VDZ selected for orbital group 1
Library entry F P VDZ selected for orbital group 1
Library entry F D VDZ selected for orbital group 1
Library entry N S VDZ selected for orbital group 2
Library entry N P VDZ selected for orbital group 2
Library entry N D VDZ selected for orbital group 2
1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990
Geometry written to block 1 of record 700
Orientation using atomic masses
Molecule type: Asymmetric top
User-specified symmetry elements: X
Symmetry elements: X
Rotational constants: 3.9381498 4.2799747 49.3093987 GHz
Point group Cs
ATOMIC COORDINATES
NR ATOM CHARGE X Y Z
1 F 9.00 0.000000000 -0.743618841 2.941716988
2 N 7.00 0.000000000 1.332215462 1.368598281
3 N 7.00 0.000000000 -0.027867311 -1.645793749
4 N 7.00 0.000000000 -0.295718679 -3.712889623
Bond lengths in Bohr (Angstrom)
1--2 2.604571082 2--3 3.307020480 3--4 2.084377535
(1.378279760) (1.750000000) (1.103005170)
Bond angles
1--2--3 102.87102741 2--3--4 163.09844307
NUCLEAR CHARGE: 30
NUMBER OF PRIMITIVE AOS: 108
NUMBER OF SYMMETRY AOS: 104
NUMBER OF CONTRACTIONS: 104 ( 80A' + 24A" )
NUMBER OF CORE ORBITALS: 4 ( 4A' + 0A" )
NUMBER OF VALENCE ORBITALS: 16 ( 12A' + 4A" )
NUCLEAR REPULSION ENERGY 94.71106174
Eigenvalues of metric
1 0.285E-02 0.125E-01 0.137E-01 0.148E-01 0.156E-01 0.208E-01 0.310E-01 0.411E-01
2 0.116E+00 0.163E+00 0.189E+00 0.197E+00 0.244E+00 0.412E+00 0.485E+00 0.572E+00
Contracted 2-electron integrals neglected if value below 1.0D-11
AO integral compression algorithm 1 Integral accuracy 1.0D-11
20.185 MB (compressed) written to integral file ( 24.1%)
Node minimum: 20.185 MB, node maximum: 20.185 MB
NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 8211570. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 8211570 RECORD LENGTH: 524288
Memory used in sort: 8.77 MW
SORT1 READ 10481262. AND WROTE 3779927. INTEGRALS IN 11 RECORDS. CPU TIME: 0.32 SEC, REAL TIME: 1.01 SEC
SORT2 READ 3779927. AND WROTE 8211570. INTEGRALS IN 77 RECORDS. CPU TIME: 0.43 SEC, REAL TIME: 1.63 SEC
Node minimum: 8211570. Node maximum: 8211570. integrals
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 17.74 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
2 4 0.45 500 600 700 1000
VAR BASINP GEOM BASIS
PROGRAMS * TOTAL INT
CPU TIMES * 2.22 2.17
REAL TIME * 5.38 SEC
DISK USED * 80.49 MB
**********************************************************************************************************************************
SETTING MAXSTEP = 50.00000000
DO I = 1.00000000
DO I = 1.00000000
1PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner
NUMBER OF ELECTRONS: 15+ 15-
CONVERGENCE THRESHOLDS: 1.00E-06 (Density) 1.00E-07 (Energy)
MAX. NUMBER OF ITERATIONS: 60
INTERPOLATION TYPE: DIIS
INTERPOLATION STEPS: 2 (START) 1 (STEP)
LEVEL SHIFTS: 0.00 (CLOSED) 0.00 (OPEN)
Molecular orbital dump at record 2100.2
ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS
1 0.000D+00 0.000D+00 -219.81971934 550.717573 0.000000 -0.686088 -16.967729 0
2 0.000D+00 0.255D+00 -245.71369429 431.538177 0.000000 3.790406 23.587239 0
3 0.932D-01 0.139D+00 -227.80453443 461.277215 0.000000 -9.027629 -42.391979 1
4 0.133D+00 0.148D+00 -254.90323994 398.198076 0.000000 4.955283 18.473436 2
5 0.131D+00 0.702D-01 -260.15249700 383.839291 0.000000 -2.685507 -7.754731 3
6 0.593D-01 0.507D-01 -262.29514084 382.861625 0.000000 -0.667117 -3.756611 4
7 0.199D-01 0.160D-01 -262.55187627 381.826376 0.000000 -0.388321 -1.443511 5
8 0.881D-02 0.688D-02 -262.60191168 382.664593 0.000000 -0.105559 -1.190815 6
9 0.361D-02 0.207D-02 -262.61065452 382.631632 0.000000 -0.021656 -0.829752 7
10 0.207D-02 0.864D-03 -262.61191710 382.617620 0.000000 -0.041701 -0.819905 8
11 0.784D-03 0.513D-03 -262.61236571 382.642271 0.000000 -0.028557 -0.775306 9
12 0.545D-03 0.150D-03 -262.61242708 382.654400 0.000000 -0.030393 -0.785455 9
13 0.203D-03 0.456D-04 -262.61243511 382.656357 0.000000 -0.029883 -0.784900 9
14 0.693D-04 0.180D-04 -262.61243663 382.657908 0.000000 -0.029123 -0.783941 8
15 0.323D-04 0.707D-05 -262.61243682 382.657615 0.000000 -0.029163 -0.784113 8
16 0.955D-05 0.270D-05 -262.61243686 382.657700 0.000000 -0.029185 -0.784145 8
17 0.447D-05 0.982D-06 -262.61243686 382.657584 0.000000 -0.029196 -0.784156 8
18 0.156D-05 0.346D-06 -262.61243686 382.657637 0.000000 -0.029207 -0.784156 9
19 0.603D-06 0.111D-06 -262.61243686 382.657627 0.000000 -0.029205 -0.784158 0
Final occupancy: 12 3
!RHF STATE 1.1 ENERGY -262.61243686
Nuclear energy 94.71106174
One-electron energy -548.65231208
Two-electron energy 191.32881348
Virial quotient -1.00100699
!RHF STATE 1.1 DIPOLE MOMENTS: 0.00000000 -0.02920475 -0.78415792
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 17.76 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
2 5 0.60 500 600 700 1000 2100
VAR BASINP GEOM BASIS RHF
PROGRAMS * TOTAL HF INT
CPU TIMES * 6.77 4.55 2.17
REAL TIME * 15.03 SEC
DISK USED * 81.79 MB
**********************************************************************************************************************************
1PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J. Knowles, H.-J. Werner (1984) S.T. Elbert (1988)
Number of closed-shell orbitals: 6 ( 6 0 )
Number of active orbitals: 13 ( 9 4 )
Number of external orbitals: 85 ( 65 20 )
State symmetry 1
Number of electrons: 18 Spin symmetry=Singlet Space symmetry=1
Number of states: 1
Number of CSFs: 71947 ( 256033 determinants, 511225 intermediate states)
State symmetry 2
Number of electrons: 18 Spin symmetry=Triplet Space symmetry=2
Number of states: 1
Number of CSFs: 117180 ( 183996 determinants, 368082 intermediate states)
Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Wavefunction dump at record 2140.2
Convergence thresholds 0.10E-05 (gradient) 0.10E-07 (energy) 0.10E-02 (step length)
Weight factors for state symmetry 1: 0.50000
Weight factors for state symmetry 2: 0.50000
Number of orbital rotations 1109 ( 54 Core/Active 390 Core/Virtual 0 Active/Active 665 Active/Virtual)
Total number of variables = 441138
ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME
1 50 56 0 -262.72812367 -262.78989193 -0.06176826 0.14768415 0.00040818 0.01106035 0.62D+00 157.07
2 82 44 0 -262.78964918 -262.79000281 -0.00035363 0.03532524 0.00000000 0.00024500 0.27D-01 361.35
3 74 44 0 -262.79000452 -262.79000456 -0.00000005 0.00024348 0.00000000 0.00000105 0.48D-03 559.05
4 74 44 0 -262.79000456 -262.79000456 0.00000000 0.00000006 0.00000000 0.00000118 0.15D-06 777.09
** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.73D-09
SOLVING CP-MCSCF EQUATIONS FOR STATE 1.1
REQUESTED ACCURACY OF CP-SOLUTION: 0.10D-06
CONVERGENCE REACHED IN 35 ITERATIONS ( 0 RESTARTS, 35 EXPANSION VECTORS), ACCURACY= 0.94D-07
SA-Gradient information saved on record 5101.1
SOLVING CP-MCSCF EQUATIONS FOR STATE 1.2
REQUESTED ACCURACY OF CP-SOLUTION: 0.10D-06
CONVERGENCE REACHED IN 35 ITERATIONS ( 0 RESTARTS, 35 EXPANSION VECTORS), ACCURACY= 0.94D-07
SA-Gradient information saved on record 5102.1
First order spin density matrix for state 1.1 saved on record 2140.2 (density set 1)
First order charge density matrix for state 1.1 saved on record 2140.2 (density set 2)
Results for state 1.1
---------------------
!MC STATE 1.1 ENERGY -262.79439994
Nuclear energy 94.71106174
Kinetic energy 262.72816993
One electron energy -548.81039165
Two electron energy 191.30492998
Virial ratio 2.00025209
!MC STATE 1.1 DIPOLE MOMENTS: 0.00000000 -0.13645621 -0.61286617 a.u. 0.000000 -0.346814 -1.557648 Debye
First order spin density matrix for state 1.2 saved on record 2140.2 (density set 3)
First order charge density matrix for state 1.2 saved on record 2140.2 (density set 4)
Results for state 1.2
---------------------
!MC STATE 1.2 ENERGY -262.78560919
Nuclear energy 94.71106174
Kinetic energy 263.31582840
One electron energy -549.24444042
Two electron energy 191.74776949
Virial ratio 1.99798638
!MC STATE 1.2 DIPOLE MOMENTS: 0.00000000 -0.01514913 -0.38102333 a.u. 0.000000 -0.038503 -0.968401 Debye
State-averaged charge density matrix saved on record 2140.2 (density set 5)
State-averaged spin density matrix saved on record 2140.2 (density set 6)
!MC EXPECT. VALUE <1.1|DMY|1.1> -0.13645621 A.U. -0.34681437 DEBYE
!MC EXPECT. VALUE <1.2|DMY|1.2> -0.01514913 A.U. -0.03850274 DEBYE
!MC EXPECT. VALUE <1.1|DMZ|1.1> -0.61286617 A.U. -1.55764841 DEBYE
!MC EXPECT. VALUE <1.2|DMZ|1.2> -0.38102333 A.U. -0.96840127 DEBYE
Natural orbital dump (state averaged) at molpro section 2140.2 (Orbital set 2)
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 22 31.76 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
5101 5102
CPSAMC CPSAMC
2 6 1.04 500 600 700 1000 2100 2140
VAR BASINP GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL MULTI HF INT
CPU TIMES * 2640.01 2633.24 4.55 2.17
REAL TIME * 5175.79 SEC
DISK USED * 349.23 MB
**********************************************************************************************************************************
1PROGRAM * FORCE (Gradient of the energy)
SA-MCSCF information from 5101.1
Orbitals from record 2140.2
Number of closed-shell orbitals: 6 ( 6 0 )
Number of active orbitals: 13 ( 9 4 )
Number of occupied orbitals: 19 ( 15 4 )
Number of electrons=30 Singlet Space symmetry=1 Wavefunction type: SA-MCSCF
End of calculation of the energy gradient ,IREST= 0
SA-MC GRADIENT FOR STATE 1.1
Atom dE/dx dE/dy dE/dz
1 0.000000000 0.000014387 -0.000032200
2 0.000000000 -0.004998875 -0.011119758
3 0.000000000 0.004939667 0.011172659
4 0.000000000 0.000044821 -0.000020701
Name= 6100 IFILE= 1
Saving a Gradient
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 23 31.76 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
5101 5102 6100
CPSAMC CPSAMC
2 6 1.04 500 600 700 1000 2100 2140
VAR BASINP GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL FORCE MULTI HF INT
CPU TIMES * 2651.65 11.64 2633.24 4.55 2.17
REAL TIME * 5199.08 SEC
DISK USED * 349.23 MB
**********************************************************************************************************************************
1PROGRAM * FORCE (Gradient of the energy)
SA-MCSCF information from 5102.1
Orbitals from record 2140.2
Number of closed-shell orbitals: 6 ( 6 0 )
Number of active orbitals: 13 ( 9 4 )
Number of occupied orbitals: 19 ( 15 4 )
Number of electrons=30 Triplet Space symmetry=2 Wavefunction type: SA-MCSCF
End of calculation of the energy gradient ,IREST= 0
SA-MC GRADIENT FOR STATE 1.2
Atom dE/dx dE/dy dE/dz
1 0.000000000 -0.005062393 0.011329011
2 0.000000000 -0.075377581 -0.152762841
3 0.000000000 0.096215285 0.134140885
4 0.000000000 -0.015775311 0.007292945
Name= 6100 IFILE= 1
Saving a Gradient
Record is complete.
NAtoms 4 NParam 12
In ReadStuff, I read these vectors ...
Gradient Difference
0.0000000000 -0.0050767797 0.0113612114
0.0000000000 -0.0703787055 -0.1416430836
0.0000000000 0.0912756174 0.1229682257
0.0000000000 -0.0158201322 0.0073136464
Energy Difference at present geometry -0.0087907462
No Derivative Coupling will be used
Upper State Gradient
0.0000000000 -0.0050623926 0.0113290111
0.0000000000 -0.0753775808 -0.1527628413
0.0000000000 0.0962152848 0.1341408847
0.0000000000 -0.0157753114 0.0072929454
Gradient inside Branching Plane
0.0000000000 -0.0004035245 0.0009030385
0.0000000000 -0.0055940053 -0.0112584078
0.0000000000 0.0072549827 0.0097740489
0.0000000000 -0.0012574528 0.0005813204
Gradient inside Intersection Space
0.0000000000 0.0004035278 -0.0009030495
0.0000000000 0.0003957290 -0.0002626614
0.0000000000 -0.0020567079 0.0017470109
0.0000000000 0.0012574511 -0.0005812999
Final Gradient for Step
0.0000000000 0.0000000033 -0.0000000110
0.0000000000 -0.0051982763 -0.0115210692
0.0000000000 0.0051982748 0.0115210598
0.0000000000 -0.0000000018 0.0000000205
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 23 31.76 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
5101 5102 6100
CPSAMC CPSAMC
2 6 1.04 500 600 700 1000 2100 2140
VAR BASINP GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL FORCE FORCE MULTI HF INT
CPU TIMES * 2663.28 11.63 11.64 2633.24 4.55 2.17
REAL TIME * 5222.35 SEC
DISK USED * 349.23 MB
**********************************************************************************************************************************
*** Long output written to logfile /home/liuxj/fn3/75.log ***
Inactive variables: N1N2
Making model hessian for Z-matrix coordinates
Optimization in local normal coordinates
Quadratic Steepest Descent - Minimum Search
Optimization point 1
Variable Last Current Next Gradient Hessian
E(MULTI) / Hartree 0.00000000 -262.78560919 0.00000000
FN / ANG 0.00000000 1.37827976 1.37827977 -0.00000002 2.43527991
N2N1F / DEGREE 0.00000000 102.87102741 102.87102695 0.00000000 0.00004445
N2N3 / ANG 0.00000000 1.10300517 1.10300518 -0.00000004 4.78426512
N3N2N1 / DEGREE 0.00000000 163.09844307 163.09844068 0.00000000 0.00006737
Convergence: 0.00000000 (line search) 0.00000005 (total)
END OF GEOMETRY OPTIMIZATION. TOTAL CPU: 0.0 SEC
ITER. ENERGY(OLD) ENERGY(NEW) DE GRADMAX GRADNORM GRADRMS STEPMAX STEPLEN STEPRMS
1 0.00000000 -262.78560919 -262.78560919 0.00000002 0.00000002 0.00000001 0.00000004 0.00000005 0.00000001
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 23 31.76 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
5101 5102 6100
CPSAMC CPSAMC
2 6 1.04 500 600 700 1000 2100 2140
VAR BASINP GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL OPT FORCE FORCE MULTI HF INT
CPU TIMES * 2663.29 0.01 11.63 11.64 2633.24 4.55 2.17
REAL TIME * 5222.36 SEC
DISK USED * 349.23 MB
**********************************************************************************************************************************
FN / ANG = 1.37827977
N1N2 / ANG = 1.75000000
N2N3 / ANG = 1.10300518
N2N1F / DEGREE = 102.87102695
N3N2N1 / DEGREE = 163.09844068
E = E
MULTI MULTI HF-SCF
-262.78560919 -262.79439994 -262.61243686
**********************************************************************************************************************************
Variable memory released
tmp = /home/liuxj/pdir//usr/local/lib/molpro-mpp-Linux-i686-i4-2002.6/molprop_2002_6_athlon_tcgmsg.exe.p
Creating: host=hartree, user=liuxj,
file=/usr/local/lib/molpro-mpp-Linux-i686-i4-2002.6/molprop_2002_6_athlon_tcgmsg.exe, port=34567
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