Posts by andrzejek

andrzejek · Quantum Chemistry

Hello,

I’m reaching out here because I couldn’t get a clear answer from the developer’s forum.

I’m calculating ESD-associated rates like kF, kP, kISC, and kIC using the adiabatic Hessian model, thoroughly accounting for H-T, Duschinsky rotation, and generally following the suggestions provided in Manual.

Unfortunately, the K*K value is quite large — at least 18 — which prevents the proper application of the output. So far, I’ve tried the following options:
- COORDSYS CART
- IFREQFLAG REMOVE TCUTFREQ 100
- IFREQFLAG REMOVE TCUTFREQ 200

…but without success.

For testing purposes, I set:
- IFREQFLAG REMOVE TCUTFREQ 500

…but the K*K value only dropped by 1 unit.

Initially, I thought the issue might be related to hydrogen atom transfer between two adjacent residues. However, in some cases where the hydrogen is on residue 1 in one state and on residue 2 in the other, the K*K values were small — around 2-3 at most — so that doesn’t seem to be the cause. Moreover, the structure remains nearly the same between the states, with little geometric alteration.

Despite that, using USEB FALSE did not improve the K*K value, nor did setting STEPCONSTR 27 (where 27 is the [Avogadro]-1 index of the hydrogen being swapped).

Any advice or suggestions would be greatly appreciated.

Thanks!

EXAMPLE:

------------------------------------------------------------------------------
                           ORCA EXCITED STATE DYNAMICS
------------------------------------------------------------------------------

Requested calculation:                         ...ISC
Coordinate system:                             ...Deloc. Internal (BAKER)
Lineshape function:                            ...Gaussian
Excited state PES:                             ...adiabatic hessian
Apply Duschinsky rotation:                     ...yes
Use operator derivatives:                      ...yes
Convert derivatives between states:            ...no
Use same frequencies:                          ...no
Multiroot calculation:                         ...no
Single mode calculation:                       ...no
Selected mode calculation:                     ...no

Initial state hessian:                         S1.hess
Reading initial state hessian:                 ...done
Final state hessian:                           T3.hess
Reading final state hessian:                   ...done

As a TS Hessian was given, HessFlag is now AH!
Adjusting all geometries to center of mass:     ...done
Rotating the excited state geometry:           ...done
The RMSD is:                                   0.085143

Writing FS hessian to:                         kISC_1.FS.hess
Calculating Wilson’s B Matrix:                 ...done
Converting to internal coordinates:            ...done
Calculating rotation matrix J:                 ...done
Calculating displacement vector K:             ...done
The sum of K*K is:                             12.855153
WARNING! Something might be seriously wrong here.
Please check the manual about large values of K*K.

andrzejek · Multiwfn and wavefunction analysis

Thanks... Well... As depicted the excitation nature fro S2->T1 is pi -> pi*, and for T0->T1 it is also pi->pi*... nothing changes, yet SOC is high

andrzejek · Multiwfn and wavefunction analysis

Dear Tian Lu,
Apologizes. I might have forgot about your previous response. Electron density difference... So maybe difference between two excited states would be ok? (4.18.13) ...or biorthogonalization of the orbitals
The point is, I dont know why S1->T2 and S2->T1 and ->T3 have so large SOC although the symmetry of orbitals doesnt change

andrzejek · Multiwfn and wavefunction analysis

Dear Tian Lu,
So how with Multiwfn I could visualize orbitals shift upon ISC from Sn to Tm state? NTOs? Though how?

andrzejek · Multiwfn and wavefunction analysis

Hello
Can HOLE-ELECTRON analysis be used to examine how orbitals changes during intersystem crossing. I specifically means to check whether ElSayed rule applies. How to do that, would be thankful for the simple example.
Thanks.

andrzejek · Quantum Chemistry

Okey, thanks anyway !

andrzejek · Quantum Chemistry

Hello Tian Lu,
For the options available here (https://www.faccts.de/docs/orca/6.0/man … cpscf.html), I tried with DIIS and CG as different solvers but fails.
Wondering what else I could change not to alters results too much?

andrzejek · Quantum Chemistry

Hello,

My input:

! bl3yp ma-def2-tzvp d4
! tightscf pal8
! opt freq smd(water)
%maxcore 4000
*xyzfile -2 2 excited-state-ea.xyz

Fails at "POPLE LINEAR EQUATION SOLVER":

POPLE LINEAR EQUATION SOLVER
----------------------------

  ITERATION   0:   ||err||_max =   3.6591e+17 (  31.6 sec   0/ 87 done)
  ITERATION   1:   ||err||_max =   1.1252e+05 (  31.2 sec   0/ 87 done)
  ITERATION   2:   ||err||_max =   2.7495e+04 (  31.3 sec   0/ 87 done)
  ITERATION   3:   ||err||_max =   3.3596e+04 (  31.4 sec   0/ 87 done)
  ITERATION   4:   ||err||_max =   4.2711e+04 (  31.3 sec   0/ 87 done)
  ITERATION   5:   ||err||_max =   4.1965e+04 (  31.3 sec   0/ 87 done)
  ITERATION   6: Error in Gauss_Jordan! Trying to shrink linear equation system (ipert=0, ndel=0)...
  ||err||_max =   2.7710e+04 (  31.0 sec   0/ 87 done)
  ITERATION   7:   ||err||_max =   1.4035e+05 (  31.2 sec   0/ 87 done)
  ITERATION   8:   ||err||_max =   5.3829e+04 (  31.1 sec   0/ 87 done)
  ITERATION   9:   ||err||_max =   8.8313e+04 (  31.1 sec   0/ 87 done)
  ITERATION  10:   ||err||_max =   3.3614e+06 (  30.8 sec   0/ 87 done)
  ITERATION  11:   ||err||_max =   1.0903e+05 (  31.0 sec   0/ 87 done)
  ITERATION  12:   ||err||_max =   2.8663e+04 (  31.1 sec   0/ 87 done)
  ITERATION  13:   ||err||_max =   2.2210e+06 (  31.0 sec   0/ 87 done)
  ITERATION  14:   ||err||_max =   1.5218e+05 (  31.1 sec   0/ 87 done)
  ITERATION  15:   ||err||_max =   8.2094e+04 (  31.0 sec   0/ 87 done)
  ITERATION  16:   ||err||_max =   6.3497e+04 (  31.2 sec   0/ 87 done)
  ITERATION  17:   ||err||_max =   7.8714e+05 (  31.1 sec   0/ 87 done)
  ITERATION  18:   ||err||_max =   1.0635e+05 (  31.2 sec   0/ 87 done)
  ITERATION  19:   ||err||_max =   1.8134e+04 (  31.2 sec   0/ 87 done)
  ITERATION  20:   ||err||_max =   2.0301e+04 (  31.3 sec   0/ 87 done)
  ITERATION  21:   ||err||_max =   1.0639e+05 (  31.1 sec   0/ 87 done)
  ITERATION  22:   ||err||_max =   5.4573e+04 (  31.1 sec   0/ 87 done)
  ITERATION  23:   ||err||_max =   1.8056e+05 (  31.2 sec   0/ 87 done)
  ITERATION  24:   ||err||_max =   1.2205e+05 (  31.1 sec   0/ 87 done)
  ITERATION  25:   ||err||_max =   4.5604e+04 (  30.9 sec   0/ 87 done)
  ITERATION  26:   ||err||_max =   7.2419e+04 (  31.1 sec   0/ 87 done)
  ITERATION  27:   ||err||_max =   3.3379e+04 (  31.4 sec   0/ 87 done)
  ITERATION  28:   ||err||_max =   2.6386e+04 (  31.2 sec   0/ 87 done)
  ITERATION  29:   ||err||_max =   1.7732e+04 (  31.1 sec   0/ 87 done)
  ITERATION  30:   ||err||_max =   9.2973e+03 (  31.2 sec   0/ 87 done)
  ITERATION  31:   ||err||_max =   6.8638e+03 (  31.3 sec   0/ 87 done)
  ITERATION  32:   ||err||_max =   3.7657e+05 (  31.3 sec   0/ 87 done)
  ITERATION  33:   ||err||_max =   1.7337e+05 (  31.4 sec   0/ 87 done)
  ITERATION  34:   ||err||_max =   1.4979e+05 (  31.5 sec   0/ 87 done)
  ITERATION  35:   ||err||_max =   7.8054e+04 (  31.3 sec   0/ 87 done)
  ITERATION  36:   ||err||_max =   2.4582e+04 (  31.3 sec   0/ 87 done)
  ITERATION  37:   ||err||_max =   2.1026e+04 (  31.3 sec   0/ 87 done)
  ITERATION  38:   ||err||_max =   2.5480e+04 (  31.5 sec   0/ 87 done)
  ITERATION  39:   ||err||_max =   4.7503e+04 (  31.6 sec   0/ 87 done)
  ITERATION  40:   ||err||_max =   1.7864e+04 (  31.5 sec   0/ 87 done)
  ITERATION  41:   ||err||_max =   1.5097e+04 (  31.6 sec   0/ 87 done)
  ITERATION  42:   ||err||_max =   4.1668e+04 (  31.6 sec   0/ 87 done)
  ITERATION  43:   ||err||_max =   1.1161e+04 (  31.5 sec   0/ 87 done)
  ITERATION  44:   ||err||_max =   1.0860e+04 (  31.9 sec   0/ 87 done)
  ITERATION  45:   ||err||_max =   1.2447e+04 (  31.9 sec   0/ 87 done)
  ITERATION  46:   ||err||_max =   1.1827e+05 (  31.9 sec   0/ 87 done)
  ITERATION  47:   ||err||_max =   1.2149e+06 (  31.6 sec   0/ 87 done)
  ITERATION  48:   ||err||_max =   1.0375e+06 (  31.8 sec   0/ 87 done)
  ITERATION  49:   ||err||_max =   3.4252e+04 (  31.8 sec   0/ 87 done)
  ITERATION  50:   ||err||_max =   1.7373e+04 (  31.9 sec   0/ 87 done)
  ITERATION  51:   ||err||_max =   1.3876e+04 (  31.8 sec   0/ 87 done)
  ITERATION  52:   ||err||_max =   2.2025e+05 (  32.2 sec   0/ 87 done)
  ITERATION  53:   ||err||_max =   1.5354e+04 (  32.0 sec   0/ 87 done)

This holds not true for the job without TIGHTSCF but I use it thoroughly so cannot just get rid of it...
What could I do about it?

Thanks.

andrzejek · Quantum Chemistry

I use Orca. LC-wPBE is not available. On the other hand, double hybrids are too expensive, I believe. Would love to sth like TPSSh but cannot due to the linear dependence as I told. And, as I said earlier, only O3LYP and TPSSh yielded reasonable vertical excitation energies so least their use is validated. I tested b3lyp, b3lyp/g, b3pw91, b97, bhandhlyp, cam-b3lyp, lc-blyp, lc-pbe, m06, m062x, m06l, o3lyp, pbe0, revTPSS, tpss, tpssh,wb97, wb97x, x3lyp...

andrzejek · Quantum Chemistry

3 Degree of agreement with the experiment should never be simply taken as the sole criterion for selecting the functional. One should consider all possible sources of discrepancy with experimental observation (e.g. conformation, solvation effect, protonation state, vibronic effect, double-excitation, and so on)

Yes, I am aware of that but right now referring solely to the excitation which is probably the most relevant at the moment of discussing whether O3LYP is fine?

andrzejek · Quantum Chemistry

Dear Tian,

To calculate electron affinity, diffuse functions are absolutely needed.

That's why I switched from the regular def2-TZVP to ma-def2-TZVP. Apparently, on another forum, people are arguing that Karlsruhe's basis sets are developed in a way that they don’t require diffuse functions as much as, for example, Pople’s basis sets. As many options exist, there are as many opinions... However, to avoid receiving negative comments from reviewers, I decided to stick with an augmented basis set.

aug-cc-pVDZ is not expensive. Dunning's basis sets are not preferential choice for DFT calculation of thermodynamic data, but for electron excitation studies, it is usable.

Okay, but shouldn’t I actually use aug-cc-pVTZ? I read somewhere that "For DFT calculations, the aug-cc-pVnZ basis set family may not be the best choice (non-ideal contraction for DFT, overly large and often poor SCF energies)". My system is also relatively small, with no more than 30 heavy atoms.

O3LYP is a rarely used functional, I do not recommend it. Generally, for calculating electronic absorption spectrum, DFT functionals with HF composition lower than 20% are not recommended, because excitation energies are usually notably underestimated. O3LYP only contains 11.61% HF composition.

I am aware that O3LYP is uncommon, but only it and TPSSh yield reasonable excitation energies compared to other functionals—no more than 10 nm greater than experimental results. I tested a bunch of them.

andrzejek · Quantum Chemistry

Dear Tian,
Thanks for your suggestions. I might indeed check with (1) and (3). On the other hand, (2) doesn't seem legit if I study anion and later will compute electron affinities, does it? Option (4) also sound reasonable, my system is not so big, but aren't Dunning basis set quite demanding and less efficient in DFT and SCF procedure? Have read somewhere about it.

In the meantime, I checked some simpler functional - O3LYP instead of TPSSh and as for now looks fine. Given the absorption spectrum are coherent with the experimental one, I suppose the swap is validated?

Best,

andrzejek · Quantum Chemistry

Hi,
I study a system contained of C, H and O in its neutral and anions forms in Orca 6. Therefore, I decided to use ma-def2-TZVP basis set. While optimization goes fine, generation of the absorption spectra fails at Davidson Diagonalization procedure. I tried using AutoAux and def2J but without a success. This is an aromatic system so I cannot limit diffused basis set just to oxygens undergoing deprotonation. What else could I do? My main route part is:

! LibXC(TPSSh) ma-def2-TZVP AutoAux TightSCF D4 SMD(H2O)

Thanks

------------------------
DAVIDSON-DIAGONALIZATION
------------------------

Dimension of the eigenvalue problem            ...  34500
Number of roots to be determined               ...     40
Maximum size of the expansion space            ...    400
Maximum number of iterations                   ...    100
Convergence tolerance for the residual         ...    2.500e-07
Convergence tolerance for the energies         ...    2.500e-07
Orthogonality tolerance                        ...    1.000e-14
Level Shift                                    ...    0.000e+00
Constructing the preconditioner                ... o.k.
Building the initial guess                     ... o.k.
Number of trial vectors determined             ...    400


                       ****Iteration    0****
   Time for iteration     :  TOTAL=69.2 TRAFO=1.2 RIJ=6.8 COSX=27.6 XC=21.4
   Size of expansion space: 120
   Lowest Energy          : -94740.194830773849
   Maximum Energy change  : 94740.194830773849 (vector 0)
   Maximum residual norm  : 1023356330656.517578125000

andrzejek · Multiwfn and wavefunction analysis

Thank you. Will check that out.
How about plotting such graphic in Chimera (not ChimeraX). Do you have a working formula for that?
Best

andrzejek · Multiwfn and wavefunction analysis

Dear All,

I am generating an NCI graphic using Multiwfn with the following input:

Multiwfn orca-optimized.molden.input << EOF
20
1
3
3
2
EOF

Despite selecting the high-quality grid option (option 3), the output appears to be of low quality:

Could anyone provide guidance on resolving this issue?

// Also, maybe there's an option to generate such in Chimera instead of VMD?

Thank you

andrzejek · Multiwfn and wavefunction analysis

Thanks Professor. I don't necessarily need to stick with NTO; if there's an other approach to visualize orbitals that indicate El Sayed rule happens, it's fine.

andrzejek · Multiwfn and wavefunction analysis

Thank for the answer Professor,
NTO would yield me pair of orbitals for each state - hole and particle. Does it mean, to assess the nature S1->T1 I compare particle of S1 (as a source) with hole of T1 (as a target?) or all four orbitals (but how to interpret then?)
/edit: I actually use orca so maybe there's an option to do it straightforwardly in it?
thank you

andrzejek · Multiwfn and wavefunction analysis

Hello,
I wish to examine assess whether observed large SOC values for transition from S1 to T1 state is related to the El Sayed rules. Is it possible to visualize the orbitals involved in the process using MultiWFN?
Thanks

Multiwfn forum

#1 Quantum Chemistry » Issue with High K*K Value in Orca 6.0 ESD Calculations » 2025-03-11 08:09:57

#2 Re: Multiwfn and wavefunction analysis » Hole-Electron Analysis for S1->T1 » 2025-02-01 08:22:48

#3 Re: Multiwfn and wavefunction analysis » Hole-Electron Analysis for S1->T1 » 2025-01-31 10:53:05

#4 Re: Multiwfn and wavefunction analysis » Hole-Electron Analysis for S1->T1 » 2025-01-31 10:20:29

#5 Multiwfn and wavefunction analysis » Hole-Electron Analysis for S1->T1 » 2025-01-30 17:38:18

#6 Re: Quantum Chemistry » POPLE LINEAR EQUATION SOLVER cannot converge » 2025-01-28 13:56:48

#7 Re: Quantum Chemistry » POPLE LINEAR EQUATION SOLVER cannot converge » 2025-01-28 12:59:19

#8 Quantum Chemistry » POPLE LINEAR EQUATION SOLVER cannot converge » 2025-01-28 11:32:13

#9 Re: Quantum Chemistry » Davidson Diagonalization fails in Orca » 2025-01-27 08:51:02

#10 Re: Quantum Chemistry » Davidson Diagonalization fails in Orca » 2025-01-26 19:34:59

#11 Re: Quantum Chemistry » Davidson Diagonalization fails in Orca » 2025-01-26 08:17:48

#12 Re: Quantum Chemistry » Davidson Diagonalization fails in Orca » 2025-01-24 08:35:34

#13 Quantum Chemistry » Davidson Diagonalization fails in Orca » 2025-01-23 07:57:54

#14 Re: Multiwfn and wavefunction analysis » Low-quality NCI despite high quality grid » 2024-12-30 16:45:51

#15 Multiwfn and wavefunction analysis » Low-quality NCI despite high quality grid » 2024-12-30 10:34:32

#16 Re: Multiwfn and wavefunction analysis » Visualize S1->T1 ISC » 2024-12-11 16:27:34

#17 Re: Multiwfn and wavefunction analysis » Visualize S1->T1 ISC » 2024-12-10 17:15:24

#18 Multiwfn and wavefunction analysis » Visualize S1->T1 ISC » 2024-12-09 18:57:58

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