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Re^3: RO-B3LYP crashes at the first SCF cycle for 2-nitropropane radical-anion

Thomas Pijper
thomaspijper@hotmail.com


Dear Vladimir,

If the tightening of various accuracy-related parameters does not work, the problem can most likely only be resolved by deleting one of the overlapping functions. The manual has a section dedicated to partial linear dependence (pages 73-76) which provides instructions on how to do this.


Kind regards,
Thom



On Fri Jan 9 '15 9:29pm, olgerdovich wrote
------------------------------------------
>Dear Thomas,

>I'm sorry, in the previous reply I made a mistake - I used DIIS=.T. SOSCF=.F. in input too (see attach to the first message), so I applied all the recomendations from the warning about linear dependence in advance, but it didn't help

>What should I do else?
>
>
>Best regards,
>Vladimir

>On Fri Jan 9 '15 8:54pm, Thomas Pijper wrote
>--------------------------------------------
>>Dear olgerdovich,

>>The problem of the SCF not converging is due to partial linear dependence in your basis. This is a very common problem when diffuse functions are employed. Partial linear dependence is indicated by the following lines in your output:

>>

                    * * * WARNING * * *
 ------------------------------------------------------------------------------
 THE OVERLAP MATRIX HAS    1 EIGENVALUES BELOW 1.5E-04.
 THE SMALLEST OF THESE IS 4.34786E-05.
 THIS INDICATES A PARTIAL LINEAR DEPENDENCE IN YOUR ATOMIC BASIS.

 TO OBTAIN SCF CONVERGENCE MAY REQUIRE
 MORE ACCURATE INTEGRAL EVALUATION (INTTYP=HONDO, ICUT=11, ITOL=30 IN $CONTRL),
 MORE ACCURATE DIRECT SCF FOCK MATRIX FORMATION (FDIFF=.FALSE. IN $SCF), OR
 CHANGING CONVERGERS (DIIS=.T. SOSCF=.F. IN $SCF).

 EIGENVALUES BELOW 1.0D-07 PROBABLY WON'T CONVERGE.
 EIGENVALUES BETWEEN 1.0D-07 AND 1.0D-06 MAY REQUIRE
 TIGHTENING OF -NCONV- DENSITY CONVERGENCE IN $SCF.

>>Please see the manual for tips on how to solve this problem.

>>With respect to your second question, the B3LYP functional contains terms describing electron correlation so this should be accounted for. Note though that DFT may not always be accurate, for example when considering long-range electron-electron interactions.
>>
>>
>>Hope this helps.

>>Kind regards,
>>Thom
>>
>>
>>
>>On Fri Jan 9 '15 1:57am, olgerdovich wrote
>>------------------------------------------
>>>Dear colleagues,

>>>I'm a newbie in computational chemistry, but with some diligence I started learning it in relation to quite simple chemical tasks from the field of nitrocompounds and I've stumbled upon several problems. First of them is the subject of this post.

>>>When I ran geometry oprimization with hessian computing for 2-nitropropane, first at HF/6-31++G** and then at B3LYP/6-31++G** level (with starting geometry form HF-calculation), I found no problem, there were convergences to ground states.

>>>Next I ran geometry oprimization with hessian computing for 2-nitropropane radical anion at ROHF/6-31++G** and once again found no trouble. It was surprising to me that some vibrations were very intense in IR to the contrary to their analogues for neutral particle, but I assumed that it was rather reasonable taking into account concomitantly changed spin and charge. The resulting species was in ground state again.

>>>But when I started geometry oprimization (with hessian computing) for 2-nitropropane radical anion at B3LYP/6-31++G** level (with starting geometry form ROHF-calculation), run crashed on the first iteration cycle for SCF even when I indicate "maxit=99" (at higher values compilator returned error, it seemed like maxit should nor be larger then NSTEP=100 in $STATPT or just larger then 100): Energy changes started to oscillate and resulted in no convergence.

>>>Output-file is attached

>>>What may I adjust in my input to get result?
>>>Hoe can I take into account electron correlation for anion-radical like the above in general?

>>>Thank you in advance


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