[molpro-user] Ask help on molpro calculation as a new user

[Yin,Shi]

Hello Kirk,
Thanks a lot for your reply and suggestions. I tried what you suggested. The input and output files are attached.
(1) print orbitals and inspect results. I think Molpro has converged to the correct electronic states.
(2) specify the occupied and closed orbitals.
(3) use b3lyp3  in Molpro.
I still get a negative VDE (-1661.94986404-(-1661.93508265)=-0.01478139).

        UKS-SCF            UKS-SCF               OPTG(UKS)
  -1661.94986404  -1661.92823332  -1661.93508265

Is there anything wrong of my input (see below), which part I try to calculate the single point energy of the neutral cluster which with the same optg structure of ion?

{uks,b3lyp3
occ,22
closed,20
wf,42,1,2
}
{uks,b3lyp3
occ,23
closed,19
wf,42,1,4
}

Thanks a lot for your help!

Shi



--
Shi Yin
Web site: http://sites.chem.colostate.edu/bernsteinlab/SY.htm
Department of Chemistry
Colorado State University
Fort Collins, CO 80523
Phone Numbers: Office 970-491-5741; Lab -5787


________________________________
From: Peterson, Kirk <kipeters at wsu.edu>
Sent: Wednesday, December 7, 2016 9:56 AM
To: Yin,Shi
Cc: molpro-user molpro-user
Subject: Re: [molpro-user] Ask help on molpro calculation as a new user

Dear Shi Yin,

you should make sure to print your orbitals and closely inspect your results to make sure Molpro has converged to the correct electronic states. You probably have to explicitly specify the occupied and closed orbitals.  Note also that the default implementation of B3LYP in Molpro is slightly different from that in Gaussian.  I believe you should use b3lyp3  in Molpro.

best,

-Kirk

On Dec 7, 2016, at 8:32 AM, Yin,Shi <Shi.Yin at colostate.edu<mailto:Shi.Yin at colostate.edu>> wrote:

Dear Molpro folks,

I am, Shi Yin, working in Prof. Elliot Bernstein group, Chemistry department at Colorado State University. Recently, I start to use molpro to do calculation on iron sulfur negative ion clusters.

I am trying to do calculations of their theoretical first vertical detachment energies (VDE = E neutral at optimized anion geometry - E optimized anion). I start with FeS- as a test firstly.I can obtain the VDE = -1661.78663123  - (-1661.76845789) = -0.01817334 Hartree = -0.494 eV.

Because I used Gaussian previously, I compared obtained results with Gaussian, and experimental results, as listed in the following table.




Molpro

Gaussian





hf/TZVP

B3lyp/TZVP

hf/TZVP

B3lyp/TZVP

Calculated VDE of quartet anion FeS-(ground state)

2.438 eV

-0.494 eV

0.83 eV

1.43 eV

Experimental VDE of anion FeS-

1.85 eV



I am confused, because the results obtained by Molpro are very different with that obtained by Gaussian, and the Gaussian results seems more reasonable comparing with the experimental result.

Since I am a new user of Molpro, I am not sure my Molpro calculations are right or not. Could someone help me to check my input file to see if there is any problem or mistake?

Or please feel free to let me know any comments and suggestions to understand the above results listed in the table.

I will appreciate your reply and help very much!



Best regards,



Shi Yin

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