J-coupling for PbH_4 system whit dyall.cv2z basis set

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carlosgim
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J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by carlosgim » 28 Sep 2015, 04:30

Dear all,

I'm trying to get J-coupling of the PbH4 system using dyall.cv2z basis set. I take this reference: Int. Journ. Of Quant. Chem. 103, 146-153 (1999), where they get a value of J [Pb-H; PbH4] $\sim$ 1601 Hz.

However in my calculations I get a value of $\sim$ 300 Hz. I think it's a big difference and I'm not sure if it is due to this warning:

Code: Select all

 
>>>>> WARNING - RHF calculations of spin-spin coupling constants are likely to give
 >>>>> WARNING - qualitatively incorrect results !!!
or the problem are related to the incorrect use of the code?

I attached the output

Carlos

Regards
Attachments
RMN_RPA_PbH4_dyall_cv2z_dalton.out
(87.96 KiB) Downloaded 408 times

hjaaj
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by hjaaj » 28 Sep 2015, 07:36

Your IJQC refence is wrong: no volume 103 in 1999, and no article starting page 146 in vol. 103.

xiongyan21
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by xiongyan21 » 28 Sep 2015, 08:34

Based on the input prepared by Prof. Giménez, Dalton2015.1 gives the following results
Indirect spin-spin coupling between H1 _1 and Pb :
======================================================


Mass number atom 1: 1; Abundance: 99.985 %; g factor: 5.585694
Mass number atom 2: 207; Abundance: 22.100 %; g factor: 1.185166

Isotropic coupling : 405.7348 Hz
Anisotropic coupling : 12.8411 Hz
Asymmetry : 0.0001
S parameter : 12.8411 Hz
A parameter : 0.0001 Hz
Isotropic DSO contribution: 0.0352 Hz
Isotropic PSO contribution: -4.3340 Hz
Isotropic SD contribution : -0.3019 Hz
Isotropic FC contribution : 410.3355 Hz




Total Coupling Tensor in Hz
---------------------------

x y z

x 409.9952 0.000000 6.060439
y 0.000000 401.4549 0.000000
z 6.060665 0.000000 405.7541


Indirect spin-spin coupling between H1 _2 and Pb :
======================================================


Mass number atom 1: 1; Abundance: 99.985 %; g factor: 5.585694
Mass number atom 2: 207; Abundance: 22.100 %; g factor: 1.185166

Isotropic coupling : 405.7348 Hz
Anisotropic coupling : 12.8411 Hz
Asymmetry : 0.0001
S parameter : 12.8411 Hz
A parameter : 0.0001 Hz
Isotropic DSO contribution: 0.0352 Hz
Isotropic PSO contribution: -4.3340 Hz
Isotropic SD contribution : -0.3019 Hz
Isotropic FC contribution : 410.3355 Hz




Total Coupling Tensor in Hz
---------------------------

x y z

x 409.9952 0.000000 -6.060439
y 0.000000 401.4549 0.000000
z -6.060665 0.000000 405.7541


Indirect spin-spin coupling between H1 _2 and H1 _1:
======================================================


Mass number atom 1: 1; Abundance: 99.985 %; g factor: 5.585694
Mass number atom 2: 1; Abundance: 99.985 %; g factor: 5.585694

Isotropic coupling : -2.7094 Hz
Anisotropic coupling : 7.7679 Hz
Asymmetry : 0.3387
S parameter : 7.9150 Hz
A parameter : 3.7759 Hz
Isotropic DSO contribution: -7.0576 Hz
Isotropic PSO contribution: 4.8246 Hz
Isotropic SD contribution : -0.0011 Hz
Isotropic FC contribution : -0.4752 Hz




Total Coupling Tensor in Hz
---------------------------

x y z

x 2.469241 0.000000 -3.775922
y 0.000000 -4.421738 0.000000
z 3.775922 0.000000 -6.175579


Interatomic separations (in Angstrom):
--------------------------------------

Pb H1 _1 H1 _2 H3 _1 H3 _2
------ ------ ------ ------ ------
Pb : 0.000000
H1 _1: 1.741094 0.000000
H1 _2: 1.741094 2.843363 0.000000
H3 _1: 1.741071 2.843059 2.843059 0.000000
H3 _2: 1.741071 2.843059 2.843059 2.843453 0.000000


Max interatomic separation is 2.8435 Angstrom ( 5.3733 Bohr)
between atoms 5 and 4, "H3 _2" and "H3 _1".

Min HX interatomic separation is 1.7411 Angstrom ( 3.2901 Bohr)


Bond distances (Angstrom):
--------------------------

atom 1 atom 2 distance
------ ------ --------
bond distance: H1 _1 Pb 1.741094
bond distance: H1 _2 Pb 1.741094
bond distance: H3 _1 Pb 1.741071
bond distance: H3 _2 Pb 1.741071


Bond angles (degrees):
----------------------

atom 1 atom 2 atom 3 angle
------ ------ ------ -----
bond angle: H1 _1 Pb H1 _2 109.481
bond angle: H1 _1 Pb H3 _1 109.465
bond angle: H1 _1 Pb H3 _2 109.465
bond angle: H1 _2 Pb H3 _1 109.465
bond angle: H1 _2 Pb H3 _2 109.465
bond angle: H3 _1 Pb H3 _2 109.488




CPU time statistics for ABACUS
------------------------------

LINRES 00:01:17 1 %
TRP LR 02:36:45 99 %

TOTAL 02:38:08 100 %


>>>> Total CPU time used in ABACUS: 2 hours 38 minutes 8 seconds
>>>> Total wall time used in ABACUS: 2 hours 48 minutes 58 seconds

There are two warnings accompanying
2 WARNINGS have been issued by Dalton,
output from 'grep -n -i WARNING' (max 10 warnings):
2031:@ >>>>> WARNING - RHF calculations of spin-spin coupling constants are likely to give
2032:@ >>>>> WARNING - qualitatively incorrect results !!!

carlosgim
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by carlosgim » 28 Sep 2015, 12:07

hjaaj wrote:Your IJQC refence is wrong: no volume 103 in 1999, and no article starting page 146 in vol. 103.
Yes, you are right. The correct reference is this one: Theor Chem Acc (1999) 103:146-153
xiongyan21 wrote:Based on the input prepared by Prof. Giménez, Dalton2015.1 gives the following results
Isotropic coupling : 405.7348 Hz
Anisotropic coupling : 12.8411 Hz
Asymmetry : 0.0001
S parameter : 12.8411 Hz
A parameter : 0.0001 Hz
Isotropic DSO contribution: 0.0352 Hz
Isotropic PSO contribution: -4.3340 Hz
Isotropic SD contribution : -0.3019 Hz
Isotropic FC contribution : 410.3355 Hz
Yes, but those numbers are too far from the Theor Chem Acc (1999) 103:146-153 publication.

Did you use the same input?

Thanks

xiongyan21
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by xiongyan21 » 28 Sep 2015, 12:22

Sure, the input is definitely identical to yours.
Are you sure that the same basis set and the same method as those in the reference are used?

carlosgim
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by carlosgim » 28 Sep 2015, 12:29

xiongyan21 wrote:Sure, The input is definitely identical to yours.
Are you sure that the same basis set as that in the reference is used?
It's not exactly the same, in the reference they use a dyall optimized basis set and I use dyall not optimized. But I think that the difference should be less than 1000 Hz at least.

xiongyan21
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by xiongyan21 » 28 Sep 2015, 13:50

The Journal of Chemical Physics has an article entitled Relativistic four-component calculations of indirect nuclear spin-spin couplings in MH4 (M=C, Si, Ge, Sn, Pb) and Pb(CH3)(3)H (112(8):3493-3498) providing the similar result to that in your reference article.
Last edited by xiongyan21 on 28 Sep 2015, 15:22, edited 1 time in total.

carlosgim
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by carlosgim » 28 Sep 2015, 14:34

Dear xiongyan21,

I take this reference: Theor Chem Acc (1999) 103:146-153, where they get a value of J [Pb-H; PbH4] $\sim$ 1601 Hz.


Regards

kennethruud
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by kennethruud » 28 Sep 2015, 15:07

Considering that the lead basis set is explicitly given in the paper to which you compare, I would suggest first to prepare an input that matches that basis set before we search for possible errors/bugs. The triplet instability problem which is the cause for the warning message printed can give rather erratic results and thus also potentially display strong basis set dependence.


Best regards,

Kenneth

xiongyan21
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by xiongyan21 » 28 Sep 2015, 15:19

kennethruud wrote: The triplet instability problem which is the cause for the warning message printed can give rather erratic results and thus also potentially display strong basis set dependence.
Dear Prof. Ruud

Your comment is absolutely appropriate .
Last edited by xiongyan21 on 04 Feb 2016, 11:10, edited 2 times in total.

xiongyan21
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Re: J-coupling for PbH_4 system whit dyall.cv2z basis set

Post by xiongyan21 » 28 Sep 2015, 15:20

kennethruud wrote: The triplet instability problem which is the cause for the warning message printed can give rather erratic results and thus also potentially display strong basis set dependence.
[/quote]

Dear Prof. Ruud

Your comment is absolutely appropriate, because the unphysical results possibly produced may be software independent.

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