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meng...@gmail.com

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Apr 12, 2021, 11:41:45 AM4/12/21

to molpro-user

Dear Molpro users and developers,

I ran into some problems when optimized the transition states of reaction HO2+HO2=H2O2+O2(1Δ).

Here is my input file:

gprint, orbitals

memory,1000,M

gthresh, energy=1.d-8

nosym,

geometry={angstrom

O

O 1 B1

H 1 B2 2 A1

H 2 B3 1 A2 3 D1 0

O 2 B4 1 A3 3 D2 0

O 5 B5 2 A4 1 D3 0

X 5 B6 2 A5 1 D4 0

}

B1= 1.30973448

B2= 0.98066735

B3= 1.495399001000

B4= 2.79780461

B5= 1.32651975

B6= 2.18631438

A1= 104.82661469

A2= 101.22009907

A3= 101.22015426

A4= 104.45051850

A5= 51.09609302

D1= -180.00000000

D2= -180.00000000

D3= 0.00000000

D4= 180.00000000

basis=avdz

{rhf;wf,34,1,0}

{multi;closed,16;occ,18;wf,34,1,0}

!frequencies

rs2,shift=0.2

optg,root=2,grad=7

forces

{frequencies,analytical;

print,hessian;

print,low,img;}

savexyz= r8-es-ts.xyz

put,molden,r8-ts-rs2.molden

Error messages:

PROGRAMS * TOTAL FREQ FORCES OPTG RS2 MULTI RHF-SCF INT

CPU TIMES * 42552.88 3737.48 15.27 38471.76 313.49 13.53 0.39 0.70

REAL TIME * 43323.44 SEC

DISK USED * 613.51 MB (local), 6.39 GB (total)

SF USED * 428.05 MB

GA USED * 38.79 MB (max) 0.00 MB (current)

**********************************************************************************************************************************

VARIABLE R8 UNDEFINED, ASSUMING 0

VARIABLE ES UNDEFINED, ASSUMING 0

VARIABLE TS UNDEFINED, ASSUMING 0

SETTING SAVEXYZ = R8-ES-TS.XYZ

Dump information in style MOLDEN to r14-ts-rs2.molden

Molecular orbitals read from record 2140.2 Type=MCSCF/NATURAL (state 1.1)

Occupation numbers read from record 2140.2 Type=MCSCF/NATURAL (state 1.1)

Orbital energies read from record 2140.2 Type=MCSCF/NATURAL (state 1.1)

Redundancy group numbers read from rec 2140.2 Type=MCSCF/NATURAL (state 1.1)

DUMP ORBITAL 1.1 AS ORBITAL 1 occ= 2.0000 eig= -20.7582 GROUP= 2

DUMP ORBITAL 2.1 AS ORBITAL 2 occ= 2.0000 eig= -20.7351 GROUP= 2

DUMP ORBITAL 3.1 AS ORBITAL 3 occ= 2.0000 eig= -20.6217 GROUP= 2

DUMP ORBITAL 4.1 AS ORBITAL 4 occ= 2.0000 eig= -20.6146 GROUP= 2

DUMP ORBITAL 5.1 AS ORBITAL 5 occ= 2.0000 eig= -1.4864 GROUP= 2

DUMP ORBITAL 6.1 AS ORBITAL 6 occ= 2.0000 eig= -1.4664 GROUP= 2

DUMP ORBITAL 7.1 AS ORBITAL 7 occ= 2.0000 eig= -1.1513 GROUP= 2

DUMP ORBITAL 8.1 AS ORBITAL 8 occ= 2.0000 eig= -1.0631 GROUP= 2

DUMP ORBITAL 9.1 AS ORBITAL 9 occ= 2.0000 eig= -0.7807 GROUP= 2

DUMP ORBITAL 10.1 AS ORBITAL 10 occ= 2.0000 eig= -0.6945 GROUP= 2

DUMP ORBITAL 11.1 AS ORBITAL 11 occ= 2.0000 eig= -0.6591 GROUP= 2

DUMP ORBITAL 12.1 AS ORBITAL 12 occ= 2.0000 eig= -0.6013 GROUP= 2

DUMP ORBITAL 13.1 AS ORBITAL 13 occ= 2.0000 eig= -0.5556 GROUP= 2

DUMP ORBITAL 14.1 AS ORBITAL 14 occ= 2.0000 eig= -0.4366 GROUP= 2

DUMP ORBITAL 15.1 AS ORBITAL 15 occ= 1.9828 eig= -0.7159 GROUP= 3

DUMP ORBITAL 16.1 AS ORBITAL 16 occ= 1.9605 eig= -0.8805 GROUP= 3

DUMP ORBITAL 17.1 AS ORBITAL 17 occ= 1.0401 eig= -0.2334 GROUP= 3

DUMP ORBITAL 18.1 AS ORBITAL 18 occ= 0.9599 eig= -0.2166 GROUP= 3

DUMP ORBITAL 19.1 AS ORBITAL 19 occ= 0.0405 eig= 0.4507 GROUP= 3

DUMP ORBITAL 20.1 AS ORBITAL 20 occ= 0.0162 eig= 0.8374 GROUP= 3

Total charge: 34.000000

Frequency information read from record 5400.2

**********************************************************************************************************************************

RS2/aug-cc-pVDZ energy= -301.127408092590

OPTG(RS2) RS2 MULTI RHF-SCF

-301.12740809 -301.12740809 -300.39283486 -300.19802042

**********************************************************************************************************************************

Molpro calculation terminated with 1 warning(s)

My questions related to the optimization about searching the excited state TS:

1. Could you help me find the reason of this warning?

2. Is it better to consider the CAS from AOs and choose a large CAS as possible? The CAS(10,10) was also tested in the same reaction, where occurred the same problem

3. There is another problem when I searched the TS by using CASPT2 method. The optimization results tend to productions or reactants. Based on those results, I adjusted the initial geometry close to TS. However, this optimization may encounter the Multi not converge problem. I have tested different initial geometries with different CAS size. It still doesn't work. Could you please give me some suggestions?

Thanks a lot for your help!

Best wishes,

Quinn

Peterson, Kirk

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Apr 12, 2021, 12:15:55 PM4/12/21

to meng...@gmail.com, molpro-user

Hi,

the warning only arises because you used dashes in the names of your savexyz and output file for molden. The program interpreted this as you doing subtraction with (undefined) variables r8, e5, and ts. Please use underscores instead of dashes. This has nothing to do with the success (or failure) of your optimization.

regards,

-Kirk

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Hans-Joachim Werner

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Apr 12, 2021, 1:56:47 PM4/12/21

to Kirk Peterson, meng...@gmail.com, molpro-user

For clarification:

savexyz=r8_es_ts.xyz
show,savexyz

still yields a warning:

VARIABLE R8_ES_TS UNDEFINED, ASSUMING 0
SETTING SAVEXYZ = R8_ES_TS.XYZ
SAVEXYZ = R8_ES_TS.XYZ

but the final result is what you want. The proper input (as mentioned in my previous mail) is

$savexyz=r8_es_ts.xyz
show,savexyz

yielding
SETTING SAVEXYZ = R8_ES_TS.XYZ
SAVEXYZ = R8_ES_TS.XYZ

Alternatively,

savexyz='r8_es_ts.xyz'
show,savexyz

or

$savexyz='r8_es_ts.xyz'
show,savexyz

both yield
SETTING SAVEXYZ = r8_es_ts.xyz
SAVEXYZ = r8_es_ts.xyz

This is because all input that is not in quotes is internally converted to upper case. Strings in quotes are left as given.
A dollar in front of the variable name indicates that it is a string variable.

Joachim

> To view this discussion on the web, visit https://groups.google.com/d/msgid/molpro-user/F8B41A2B-B7DC-44A0-B8E5-6376E7B23583%40wsu.edu.

Quinn Wang

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Apr 12, 2021, 1:56:55 PM4/12/21

to Hans-Joachim Werner, Kirk Peterson, molpro-user

Dear Prof. Werner and Prof. Peterson,

Thanks a lot for all of your clarifications.

I commented this line r8_es_ts.xyz and run it again. The warning still exists. Actually, I have copied the optimized geometry as another initial guess for TS optimization at rs2/aug-cc-pvtz level, of which the result is far from the TS on the contrary. I was wondering if there is something wrong with my setting of the CAS or I should specify some key words to promote the TS optimizations.

Thanks!

Best regards,

Quinn

Hans-Joachim Werner <wer...@theochem.uni-stuttgart.de> 於 2021年4月12日週一下午12:29寫道：

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