What is the keyword in NWCHEM to calculate reorganization energies
Forum Vet
8:52:49 PM PST - Fri, Dec 7th 2018
Dear All
Since 2016 or perhaps 2014, GAMESS has added the function to calculate reorganization energies of ET and proton-coupled ET reactions, published, respectively, until 2014, where one of the two necessary steps may fail on an old cpu, in the cases of electrode plus solvent, electrode plus self assembled monolayer and solvent, electrode plus double layer and ionic solution, and homogeneous solvent, respectively, which also has an equivalent Python program. This original program were contributed to GAMESS by Profs. and Drs. previously in the world-wide famous Department of Chemistry of University of Illinois at Urbana-Champaign and evaluated aassembled into the existing solvation module of gamess by Profs and Drs. in Prof. Gordon's Group and Ames Laboratory. According to the authors' paper on SAM monolayer modified electrodes, they can produce total reorganization energies in good agreement with experimental data for all 12 metal complexes tested in aqueous solution, useful for molecular electrocatalysts electron transfer rate constants calculation.

It is said in the NWCHEM manual that it also can calculate reorganization energies, but I cannot find any keyword or example about this.
How to do it in NWCHEM?
Thanks a lot!

Very Best Regards!

Forum Vet
9:17:45 AM PST - Wed, Dec 19th 2018
First, I need calibrate it using published experimental data or theoretical results. I find the calculated average reorganization energies of hydroquinone oxidation and the corresponding reduction state in the situation of electrode plus double layer and an ionic aprotic solution, the sole environment chosen for now, is only around 0.09 eV deviating from the outer sphere one obtained with a different method in a published paper in 2004, one of whose author was at EMSL then, using Gaussian98, with the same functional, i.e., B3LYP in the VMN3 case in GAMESS without TDA, although the solvent there may be different from what I have tested. Perhaps the new module is more accurate in some cases.

Forum Vet
9:08:26 PM PST - Sat, Jan 12th 2019
Thanks a lot for a professor's answer on Github.
Now ET rate constants can be got from MARCUS's theory using GAMESS and NWCHEM perhaps integrately.

Forum Vet
7:17:00 AM PST - Wed, Feb 6th 2019
MP2 6-31g(d,p) MP2 optimized hydroquinone has no warning for HESSIAN using GAMESS whose outer reorganization in another solvent is within 0.05 eV deviating from the previously mentioned article.

Forum Vet
10:19:22 PM PST - Fri, Feb 8th 2019
The dftb3 optimized hydroquinoe has no warning for the HESSIAN using GAMESS, and the outer reorganization enegy in another solvent is in good agreement with that in the previously metioned article, i.e., the difference is within 0.06eV.


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