Multiwfn official website: http://sobereva.com/multiwfn. Multiwfn forum in Chinese: http://bbs.keinsci.com/wfn
You are not logged in.
sobereva wrote:atmraddens.f90 file can be found in the source code package of Multiwfn, in this file you can find "subroutine genatmradpos", which defines radial density for all elements. After replacing the existing data of Tb by the data in sphavgval.txt, you need to recompile Multiwfn to make the modification take effect.
Thank you, I really appreciate the guidance. The Ln complexes are trivalent though. Do I need to generate the reference densities in this Oxidation state, i.e. as Ln(III)? Or in the neutral ground state configuration.
must in the neutral ground state configuration, according to the definition of Hirshfeld method
atmraddens.f90 file can be found in the source code package of Multiwfn, in this file you can find "subroutine genatmradpos", which defines radial density for all elements. After replacing the existing data of Tb by the data in sphavgval.txt, you need to recompile Multiwfn to make the modification take effect.
Calculation of Hirshfeld charges needs electron density of atoms in their isolated states. However, there is no unique way of generating them. I am not sure how ORCA developers generated them and cannot comment on it, what I can say is that the Hirshfeld charge in Multiwfn was implemented in a very rigorous way, and the quality of built-in atomic densities in isolated states has a very high quality (see Section 6.3 of Multiwfn manual for details). So, as long as the wavefunction and structure you provided to Multiwfn are correct, and the commands you inputted in Multiwfn are correct, the Hirshfeld charges computed by Multiwfn must be correct.
BTW: It is suggested to first check if Mulliken charges calculated by Multiwfn and ORCA are the same; if they are the same, that means the wavefunction has been correctly passed to Multiwfn.
Hello,
You can use main function 5 of Multiwfn to calculate grid data for a real space function, then in the post-processing menu, you can choose to export the grid data as the very popular .cub file. See Section 4.5 of Multiwfn manual for examples.
I don't have any experience in using VMD 2.0, and I would still use VMD 1.9.3 in the near future. It should be noted that VMD 2.0 has not been formally released, currently there is only a pre-release version. I will try 2.0 only when the formal version is released.
The steps are seemingly correct.
Please note that when calculating the monomers in Gaussian, "nosymm" keyword should be used to prevent Gaussian from automatically reorientating the system coordinate, otherwise the coordinates of the monomers will finally overlap with each other, and thus the calculated exciton coupling will be completely wrong.
Please only focused on how /auto affects relative energies, e.g. reaction energies and barriers. If this change is indeed significant, perhaps /auto in Gaussian is not well compatible with pseudopotential basis sets, it is suggested to use an all-electron basis set for TM instead and then check if the influence by /auto is in a reasonable range.
Additional question: For single-point energy calculation using an ordinary functional, if I want to compare the performance of the following Pople-type basis sets (6-31g*, 6-311g**, 6-311+g**) with def2-series (which use 5D 7F), would you say that it is more proper to use 6D 10F uniformly for all Pople-type basis sets?
To completely fairly compare accuracy of different basis sets, in principle, it is suggested to use the basis function form employed by the respective original authors of the basis sets. e.g. 6D for Pople series and 5D for def2-series. For angular moment of F or higher, spherical-harmonic form should always be used (note that even for 6-31G, 7F is used by default in Gaussian).
Gaussian by default uses 7F for all basis sets. The difference between 5D and 6D in the case of solvation energy calculation is negligible.
It's true. The effect of this approximation is usually negligible.
If you want to obtain exact total orbital interaction energy, it is suggested to use sobEDA method (J. Phys. Chem. A 2023, 127, 7023−7035). The sum of all NOCV pair contributions may be scaled to the exact value to derive slightly more accurate contribution of each NOCV pair.
Please check Section 3.10.1 of Multiwfn manual, the correspondence is given.
Traditional pure functionals like PBE and TPSS nowdays have little value for calculating isolated systems, except for transition metal clusters. In addition, when PBE and TPSS are suitable for use, using r2SCAN instead is likely a better choice.
1 Yes, but the larger the basis set, the smaller the accuracy improvement from adding diffuse functions
2 In principle, ma-TZVPP/ma-QZVPP is not suitable for basis set extrapolation, because the diffuse function part is not constructed in a systematic manner.
The answer depends on if there are atoms with significant negative charge (e.g. ADCH atomic charge < -0.5) and meantime directly participating in the reaction, it is not dependent of theoretical method. Only those atoms need diffuse functions to improve result.
However, note that if basis set extrapolation is used, the necessity of adding diffuse functions is somewhat weakened.
Hello,
There is no corresponding option in the post-processing menu of main function 4. You can simply use main function 4 to plot RDG instead of IRI.
Dear Roman,
This is because you didn't modify configuration coefficients to follow the convention of Gaussian, which is also the convention of the plain text file of Multiwfn. In the case of TDDFT of Gaussian, when reference state is closed-shell, the coefficients are normalized to 0.5 (because alpha and beta part are the same, only one of them is printed); however, in the plain text file you provided they normalize to 1.0. (In contrast, when Multiwfn directly loads configuration coefficients from ORCA output file, the convention is automatically converted).
Best regards,
Tian
1 In most case DFT works reasonably. For example, H2+H• -> H• + H2, DFT can nicely represent the whole PES.
2 MRPT is not absolutely necessary, depending on the specific reaction.
3 If transition metal is directly involved in the process, multireference treatment may be necessary, but still not always.
4 When excited state is involved, the situation is significantly more complex; whenever possible, using a proper multireference method is recommended, especially when transition metal participates in the process.
Dear Roman,
It is not a bug of Multiwfn. You forgot to fix the MO numbering convention when converting information from ORCA output to plain text file. In ORCA, MO index starts from 0, while in Multiwfn, the index starts from 1. So, all MO indices in the plain text file provided to Multiwfn must also start from 1, that means you should add all MO indices by 1 in the current plain text file.
I will modify the manual to make ORCA users aware of this point.
Best regards,
Tian
It is nothng, I'm glad to know that you finally made clear the situation.
Hello,
Multiwfn can export NMR curve data as NMR_curve.txt, which is a two-column text X-Y file, you can directly import it into e.g. Origin, or directly using gnuplot/qtgrace to plot it as a curve map.
Yes.
Perhaps it is just a bug, or the algorithm is not robust enough in rare case... (especially "downhill" is not a popular option)
Dear Alessio,
Multiwfn doesn't support SAPT. However, if you have Gaussian 16, I highly recommend to use sobEDAw energy decomposition method, which can be realized via Multiwfn in combination with Gaussian 16. See J. Phys. Chem. A 2023, 127, 7023−7035 for original paper, and http://sobereva.com/soft/sobEDA_tutorial.zip for tutorial. sobEDAw can provide very similar information to that of high-order SAPT, while the cost is significantly lower.
Best regards,
Tian
Your Multiwfn version is extremely old. Please update to the latest version.
The state 7 is dominated by MOs 174a -> 179a, if you perform NTO by Multiwfn for this state, the two NTOs of the dominate pair should quite like these two MOs. Also, the hole and electron generated by the hole-electron analysis of Multiwfn should be quite similar to 174a and 179a, respectively. Please beware that the index in ORCA output starts from 0 rather than 1 (Multiwfn).
Nonpolar part of SMD only contributes to electronic energy, you will understand this point if you read original paper of SMD. Moreover, it is independent of actual electron distribution but only dependent of coordinate, so nonpolar contributions to ground state and excited state energies are exactly the same, namely it doesn't contribute to vertical excitation energy, and doesn't affect electronic structure.
Note that the polar part of SMD is slightly different to PCM, because SMD defined a set of atomic radii focusing on reproducing experimental molecular solvation energy, these radii are commonly different to the default atomic radii used by the PCM in quantum chemistry codes under the default setting.
1 I cannot say it must be better, but w-tuned LRC has high probability better than PBE0 in this case.
2 No. The polar part of SMD is just PCM, and only polar part affects excitation energies and electronic structure of excited state.
The result is not necessarily wrong. Hyperpolarizability (beta) is often sensitive to frequency of incident light, static and dynamic beta at certain frequencies can easily differ by several times. Given that < β_HRS > contains squared beta components, it is not surprising that < β_HRS > calculated based on static and dynamic beta differ by nearly one order of magnitude.
It is indeed a misprint in the manual, I will fixed it. Thank you for pointing out.
In principle, evaluation of reorganization energies and H–R factors do not need NACME.
NACME is used by ORCA_ESD when evaluating internal conversion rate.
I seems that the elemenary step of generating D-THF is missing in the energy profile map. There should be a weakly interacting complex like TS'...THF, which corresponds to a PES minimum, and the TS' is the (unstable) molecule produced after passing through TS. THF will react with TS' to yield D-THF. Only when the complete reaction profile is constructed, the reaction rate can be estimated.
In the main function 4 of Multiwfn, there are many ways to define plotting plane, please carefully check Section 3.5.2 of Multiwfn manual. Perhaps you need to manually input coordinates of three vertices to propely define the expected plotting plane.