[CP2K-user] [CP2K:20004] Inquiry on ROKS Calculation Schemes within CP2K

[Lukas Razinkovas]

Dear Prof. Jurg,


Thank you for your response. I am currently exploring ROKS schemes to model
excited state potential energy surfaces and have several questions to
improve my understanding:

   1. Does the LOW_SPIN_ROKS approach derive from your collaboration with
   Imgrad in the study "Molecular dynamics in low-spin excited states" [J.
   Chem. Phys. 108, 10 (1998)], and its subsequent extension to accommodate
   any number of unpaired electrons [Chem. Phys. 373, 283 (2010)]?
   2. In my investigation, I calculated the quartet to doublet excitation
   energy using the von Barth/spin projection method combined with UKS,
   yielding results remarkably close to experimental data. However,
   LOW_SPIN_ROKS calculations yielded energies significantly higher than
   expected. Considering I am examining localized defect states (d orbitals of
   Chromium) in a crystal environment, localized orbitals might shift above
   the conduction band minimum. This scenario could misrepresent the
   configuration as (a b CBM) rather than the intended (a b c). Is there a way
   to investigate single-particle states within LOW_SPIN_ROKS calculations to
   address this concern?
   3. Upon reviewing Filatov's publication (Chem. Phys. Letter 288, 689
   (1998)), I understand it lays the foundation for a formal multi-determinant
   state approach within ROKS. This approach appears to be activated through
   the "ROKS_SCHEME GENERAL" setting. However, looking at the code,
   specifically "SUBROUTINE combine_ks_matrices_2," suggests its current
   implementation is limited to single-determinant solutions due to the
   absence of iterations over energy scaling parameters. Could you confirm if
   my observation is accurate?
   4. Lastly, I'd like to know whether the MOM method can be applied to
   HIGH-SPIN or GENERAL schemes. I aim to model spin-contaminated
   configurations such as |a b \bar{c}|, which seem unattainable with the
   MULTIPLICITY 2 keyword since it strictly enforces a |a \bar{a} b|
   configuration.


I appreciate your time and look forward to your replies.


Best regards,

Lukas

On Mon, Mar 4, 2024 at 3:07 PM Jürg Hutter <hutter at chem.uzh.ch> wrote:

> Hi
>
> these methods / implementations are based on the work by Irmgard Frank.
> You can find earlier work e.g. by Claude Daul and also M. Filatov.
> There has been recently some new work by other groups that is closely
> related.
>
> 1) this is for single determinant only (all excess electrons in one spin
> channel)
> 2) I think it is correct, but I would have to look more closely
> 3) ROKS was implemented before MGGAs. It seems the ROKS branch was not
> updated for these type of functionals.
> 4) See the work of Daul and Filatov
>
> regards
> JH
>
> ________________________________________
> From: cp2k at googlegroups.com <cp2k at googlegroups.com> on behalf of Lukas
> Razinkovas <lukasrazinkovas at gmail.com>
> Sent: Sunday, March 3, 2024 8:19 AM
> To: cp2k
> Subject: [CP2K:19983] Inquiry on ROKS Calculation Schemes within CP2K
>
> Dear CP2K Community,
>
>
> As a newcomer to CP2K (my experience is with VASP, GPAW, and Quantum
> Espresso), I have been exploring CP2K's capabilities, particularly for
> modeling low-spin bi- and tri-radical states of crystal defects through
> ROKS (Restricted Open-Shell) calculations for potential energy surface
> analysis. I am pleasantly surprised by this code's performance and
> capabilities.
>
>
> However, I am slightly confused with ROKS calculations within CP2K,
> especially regarding the implementation and application of its varying
> schemes, namely:
>
>
>   *   High-Spin ROKS (default ROKS_SCHEME value)
>   *   GENERAL (an alternative ROKS_SCHEME value)
>   *   Low-Spin ROKS
>
>
> I would greatly appreciate any directed literature or resources that
> elaborate on these schemes' implementation and practical use.
>
>
> Additionally, I have a few specific inquiries that I hope could be
> clarified:
>
>
>   1.  Is the High-Spin ROKS scheme tailored for single-determinant maximal
> spin states, where all unpaired electrons align in one spin direction? Can
> it also model mixed (spin-contaminated) single-determinant states for the
> von Barth/approximate spin projection method?
>   2.  For modeling the doublet state in a triradical scenario, I am
> considering the following configuration:
> &LOW_SPIN_ROKS
>   # DOBLET: E(D) = E(Q) - 3/2*E(Q) + 3/2*E(M)
>   ENERGY_SCALING -1.5 1.5
>   SPIN_CONFIGURATION 1 1 1 # Psi(Q) |a a a>
>   SPIN_CONFIGURATION 1 1 2 # Psi(M) |a a b>
> &END LOW_SPIN_ROKS
> Is this the correct approach?
>   3.  I encountered difficulties running LOW_SPIN_ROKS with the R2SCAN
> functional (however, it worked with PBE). Are there compatibility issues
> with meta-GGA functionals?
>   4.  Can the energy outcomes from maximal-spin and low-spin calculations
> be compared to deduce exchange splitting (excitation) energy?
>
>
> I look forward to any recommendations or advice you could provide.
>
>
>
> Best wishes,
>
> Lukas
>
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