BROKEN SYMMETRY
1,111 views
Skip to first unread message
Rizwan Nabi
Jun 30, 2015, 8:00:30 AM6/30/15
to cp...@googlegroups.com
Hi dear cp2k users
I have a little confusion about BS section of cp2k input.
I have a poly-metallic complex in which some of my Mn atoms are in +2 Oxidation state and while some are in +3 Oxidation state i.e Mn(III) and Mn(II). Some of my metals ions need to be down-spin while others need to be up-spin.
I tried to keep some up-spin while others down-spin but I do not know whether the values I used are correct or not. Would anyone please help me set the correct values of KEYWORD NEL in BS.
Here I am showing my combination of NEL values.
Here Mn1 = MnII SPIN-UP
Mn2 = MnIII SPIN-UP
Mn3 = MnIII SPIN-DOWN
Mn4 = MnII SPIN-DOWN
&KIND Mn1
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL 0 0
L 0 2
N 4 3
&END
&BETA
NEL -2 0
L 0 2
N 4 3
&END
&END
&END
&KIND Mn2
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL 0 0
L 0 2
N 4 3
&END
&BETA
NEL -2 -1
L 0 2
N 4 3
&END
&END
&END
&KIND Mn3
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 -1
L 0 2
N 4 3
&END
&BETA
NEL 0 0
L 0 2
N 4 3
&END
&END
&END
&KIND Mn4
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 0
L 0 2
N 4 3
&END
&BETA
NEL 0 0
L 0 2
N 4 3
&END
&END
&END
Your help will be cordially appreciated
Regards
Rizwan
S Ling
Jun 30, 2015, 9:45:15 AM6/30/15
to cp...@googlegroups.com
Hi
Please try this one instead. This is only for the initial guess. There is no guarantee that the electronic configurations will converge to what you expect after the SCF calculation. Please double check the magnetic moments on each atom after the calculation. You may find more discussion on the usage of &BS in the following post by Marcella:
SL
&KIND Mn1
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 5
L 0 2
N 4 3
&END
&BETA
NEL -2 -5
L 0 2
N 4 3
&END
&END
&END
&KIND Mn2
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 3
L 0 2
N 4 3
&END
&BETA
NEL -2 -5
L 0 2
N 4 3
&END
&END
&END
&KIND Mn3
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 -5
L 0 2
N 4 3
&END
&BETA
NEL -2 3
L 0 2
N 4 3
&END
&END
&END
&KIND Mn4
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 -5
L 0 2
N 4 3
&END
&BETA
NEL -2 5
L 0 2
N 4 3
&END
&END
&END
--
You received this message because you are subscribed to the Google Groups "cp2k" group.
To unsubscribe from this group and stop receiving emails from it, send an email to cp2k+uns...@googlegroups.com.
To post to this group, send email to cp...@googlegroups.com.
Visit this group at http://groups.google.com/group/cp2k.
For more options, visit https://groups.google.com/d/optout.
Rizwan Nabi
Jun 30, 2015, 1:22:18 PM6/30/15
to cp...@googlegroups.com
Hi S Ling
Thank you for your response
I tried the combination you gave me but I think it gives me contradictory results.
Here I am mentioning required portion of my output
where
Mn1 = MnII SPIN-UP
Mn2 = MnIII SPIN-UP
Mn3 = MnIII SPIN-DOWN
SPIN 1
Guess for atomic kind: Mn1
Electronic structure
Total number of core electrons 10.00
Total number of valence electrons 18.00
Total number of electrons 28.00
Multiplicity not specified
S [ 2.00 2.00] 2.00
P [ 6.00] 6.00
D 10.00
SPIN 2
Guess for atomic kind: Mn1
Electronic structure
Total number of core electrons 10.00
Total number of valence electrons 8.00
Total number of electrons 18.00
Multiplicity not specified
S [ 2.00 2.00] 2.00
P [ 6.00] 6.00
SPIN 1
Guess for atomic kind: Mn2
Electronic structure
Total number of core electrons 10.00
Total number of valence electrons 16.00
Total number of electrons 26.00
Multiplicity not specified
S [ 2.00 2.00] 2.00
P [ 6.00] 6.00
D 8.00
SPIN 2
Guess for atomic kind: Mn2
Electronic structure
Total number of core electrons 10.00
Total number of valence electrons 8.00
Total number of electrons 18.00
Multiplicity not specified
S [ 2.00 2.00] 2.00
P [ 6.00] 6.00
SPIN 1
Guess for atomic kind: Mn3
Electronic structure
Total number of core electrons 10.00
Total number of valence electrons 8.00
Total number of electrons 18.00
Multiplicity not specified
S [ 2.00 2.00] 2.00
P [ 6.00] 6.00
SPIN 2
Guess for atomic kind: Mn3
Electronic structure
Total number of core electrons 10.00
Total number of valence electrons 16.00
Total number of electrons 26.00
Multiplicity not specified
S [ 2.00 2.00] 2.00
P [ 6.00] 6.00
D 8.00
So would you please explain me whether the given configurations are right or wrong.
Regards
Rizwan
S Ling
Jun 30, 2015, 2:30:14 PM6/30/15
to cp...@googlegroups.com
Hi
Please have a look at the link which I mentioned earlier. The total number of electrons in each spin channel will be rescaled by a factor of 2.
SL
Rizwan Nabi
Jul 1, 2015, 12:03:14 PM7/1/15
to cp...@googlegroups.com
Hi S Ling
Thank you for your response
I think I have got an idea now. Is it right to mention NEL values for V(II) like this then as per that post. Sorry for asking same question over and again.
V(II) i.e V in +2 oxidation state will have NEL values as. Correct me if am wrong.
V1 (SPIN UP) AND V2 (SPIN DOWN)
&KIND V1
ELEMENT V
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q13
&BS
&ALPHA
NEL -2 7
L 0 2
N 4 3
&END
&BETA
NEL -2 -7
L 0 2
N 4 3
&END
&END
&END
&KIND V2
ELEMENT V
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q13
&BS
&ALPHA
NEL -2 -7
L 0 2
N 4 3
&END
&BETA
NEL -2 7
L 0 2
N 4 3
&END
Regads
Rizwan
S Ling
Jul 1, 2015, 12:29:53 PM7/1/15
to cp...@googlegroups.com
Hi
The electronic configuration of V2+ is [Ar]3d34s0. Therefore, instead of +7 and -7, you should set NEL of the 3d orbital to +3 and -3 for ALPHA and BETA spin channels, respectively. "+3" is performed on the electronic configuration of atomic V which is [Ar]3d34s2, and you end up with (3+3)/2=3 for the ALPHA spin channel. Similarly, for the BETA spin channel, you have (3-3)/2=0.
SL
--
Rizwan Nabi
Jul 1, 2015, 1:10:58 PM7/1/15
to cp...@googlegroups.com
Thank you sir for your reply.
Now things became even more clear to me.
Regards
Rizwan
Rizwan Nabi
Jul 2, 2015, 11:24:29 AM7/2/15
to cp...@googlegroups.com
Hi S Ling
I tried with the same option of BS section but I am getting some error in my output file as it does not print electron density, charges and energy. I do not know where the problem lies. Here I am attaching my output file generated. Please check it once.
Regards
Rizwan
S Ling
Jul 2, 2015, 12:02:21 PM7/2/15
to cp...@googlegroups.com
Hi
It could relate to the settings on NEL in &BS section, but without your input, I cannot say anything. Please also try the following settings. It is a little bit different from the previous one.
SL
&KIND Mn1
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 3
L 0 2
N 4 3
&END
&BETA
NEL -2 -5
L 0 2
N 4 3
&END
&END
&END
&KIND Mn2
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 1
L 0 2
N 4 3
&END
&BETA
NEL -2 -5
L 0 2
N 4 3
&END
&END
&END
&KIND Mn3
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 -5
L 0 2
N 4 3
&END
&BETA
NEL -2 1
L 0 2
N 4 3
&END
&END
&END
&KIND Mn4
ELEMENT Mn
BASIS_SET DZVP-MOLOPT-SR-GTH
POTENTIAL GTH-BLYP-q15
&BS
&ALPHA
NEL -2 -5
L 0 2
N 4 3
&END
&BETA
NEL -2 3
L 0 2
N 4 3
&END
&END
&END
--
Rizwan Nabi
Jul 3, 2015, 8:34:34 AM7/3/15
to cp...@googlegroups.com
Hi S Ling
Thank you for your valuable inputs
The new NEL values you gave me are working fine, but I just have one query about V(II) STATE do I have to use same values of NEL you have given me for V(II) or is there any change required. And would you please give a general idea of how to fix these values for any metal such that I may use that idea for future work on other metals with different multiplicity.
Here I am mentioning your comment.
The electronic configuration of V2+ is [Ar]3d34s0. Therefore, instead of +7 and -7, you should set NEL of the 3d orbital to +3 and -3 for ALPHA and BETA spin channels, respectively. "+3" is performed on the electronic configuration of atomic V which is [Ar]3d34s2, and you end up with (3+3)/2=3 for the ALPHA spin channel. Similarly, for the BETA spin channel, you have (3-3)/2=0.
Your help is cordially appreciated!
Regards
Rizwan
S Ling
Jul 3, 2015, 7:25:00 PM7/3/15
to cp...@googlegroups.com
Hi
For V(II), you can try the same values which I gave you. If it doesn't work, then please try to reduce +7/-7 to something like +5/-5. The general idea is to the break the symmetry by adding or substracting electrons from the ALPHA and BETA spin channels, and by adding/substracting differnet number of electrons from different atoms, hopefully you can get different oxidation states on different atoms after the SCF calculation. The total number of electrons should be corrected after the rescaling, but in certain cases, you might end up with more than 5 d electrons in the ALPHA or BETA spin channel even after the scaling, and therefore you see the problems you mentioned earlier. I am not very clear about how the rescaling was done. Maybe some other people on this mailing list can give you more information. I would suggest you to play with some small systems to get more feeling about it. Keep in mind that the &BS subsection just break the symmetry of your initial guess. You may or may not get the exact magnetic ordering or oxidation states which you expect after the SCF calculation, and therefore, you should always check the spin moments on different atoms after the SCF calculation.
SL
--
Rizwan Nabi
Jul 4, 2015, 2:18:47 AM7/4/15
to cp...@googlegroups.com
Hi
Thank you again for your response
I will follow your suggestions.
Rizwan
Reply all
Reply to author
Forward
0 new messages