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#1 Re: Multiwfn and wavefunction analysis » Question about MO coefficients for f+3 and f-3 shells » 2018-03-08 18:14:51

sobereva wrote:

Dear lijingbai2009,

The reason of introducing the factor of -1 is that the convention used by ORCA is very weird. For F(+3), F(-3) and G(+3) G(-3) G(+4) G(-4), the basis functions are normalized to -1 rather than 1, therefore in order to make analysis result meaningful, the corresponding LCAO coefficient must be multiplied by -1. I don't know why ORCA uses such strange convention.

Best wishes,

Tian

Dear Tian Lu,

That's the exact reason I wanted to know. ORCA does have many tricks inside. Now everything are clear for me. Thanks a lot again.

Best regards,
Jingbai

#2 Multiwfn and wavefunction analysis » Question about MO coefficients for f+3 and f-3 shells » 2018-03-07 18:53:43

lijingbai2009
Replies: 3

Dear forum,
    I've been checking the molecular orbitals loaded from molden file and got confused a little bit.

    For example, my test job was a single Pt ion with +2 charges using pbe0/def2-svp in ORCA 4.0.0. The f shell coefficient in MO 29 were "-0.000014, 0.000002,-0.391068, -0.000025,-0.000011,      -0.000016, 0.919986        ". When I used Multiwfn to print coefficient matrix, it showed "-0.000014, 0.000002,-0.391068, -0.000025,-0.000011,          0.000016, -0.919986      ". Just look at the last two numbers, they are from f+3 and f-3 shell. The first is the second multiplying -1.
    After I saved to another molden, the MO coefficients for f+3 and f-3 in the new molden file turned back as "-0.000016, 0.919986".

    Then I checked the transformation from spheric harmonic type GTO to cartesian ones. I found if I don't multiply the MO coefficient for f+3 and f-3 shell by -1, my results would be totally wrong. After multiplying by -1, the pure f shell can be correctly transfer to cartesian f shell.

   So my question is, where is this -1 from?

Best regards,
Jingbai

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