[adf-list] Adflist Digest，第23卷，问题1
Mitoraj. Mitoraj在Chemia.uj.edu.plFueb 9 12:34:05 CET 2016
- 以前的消息（按线程）： [adf-list] Adflist Digest，第23卷，问题1
- 下一条消息（按线程）： [adf-list]帮助 消息排序： [ 日期 ] [ 线 ] [ 主题 ] [ 作者 ]
Hi Mark and Tobias, Indeed, Alexei is right, the remaining 4.3 kcal/mol originates from the remaining NOCV pairs; they are summed at the end of SFO section; in order to get the corresponding NOCV deformation density one can substract the most important channels from the overall deformation density (density-densties of orthogonalized fragments); very best greetings, Mariusz W dniu 2016-02-09 10:18, Alexei Yakovlev napisaÅ‚(a): > Hi Mark, > > Tobias is absolutely correct about the source of the -33 vs. -37 > kcal/mol discrepancy. It has nothing to do with the calculation > accuracy but is caused by the fact that only the top 8 pairs are used > to obtain the -33.41 number. The other 480 pairs are most likely > responsible for the remaining 4.3 kcal/mol. > > Alexei > > On 08/02/2016 17:23, Marc Raupach wrote: > >> Dear Tobias, >> >> I am happy that my answer was useful. Nevertheless, I would like to >> point something out which is maybe still unclear. >> >>> Orbital Interactions: >>> A: -37.77 >>> -------------- >>> Total -37.77 (kcal / mol) >> This energy is calculated solely by the ETS method in the basis of >> the orthogonalized fragment orbitals. >> >>> ETS-NOCV-decomposition: taken restricted fragments >>> =================================================== >>> >>> 1. Eigenvalue pairs from diagonalization of DeltaP expressed in >>> Lowdin: >>> 1 -0.45650 976 0.45650 >>> 2 -0.26709 975 0.26709 >>> 3 -0.26685 974 0.26685 >>> 4 -0.18012 973 0.18012 >>> 5 -0.05494 972 0.05494 >>> 6 -0.05493 971 0.05493 >>> 7 -0.05253 970 0.05253 >>> 8 -0.05240 969 0.05240 >>> 2. Orbital Interaction Energy Contributions from each NOCV pair >>> (in a.u.) >>> 1 -0.02352 >>> 2 -0.00958 >>> 3 -0.00957 >>> 4 -0.00848 >>> 5 -0.00078 >>> 6 -0.00078 >>> 7 -0.00026 >>> 8 -0.00026 >>> 3. Orbital Interaction Energy Contributions from each NOCV pair >>> (in kcal/mol) >>> 1 -14.76153 >>> 2 -6.01314 >>> 3 -6.00468 >>> 4 -5.32319 >>> 5 -0.49070 >>> 6 -0.48816 >>> 7 -0.16481 >>> 8 -0.16229 >> These energy terms are calculated by the ETS method in the basis of >> the NOCV orbitals. So an additional basis transformation is carried >> out, which by itself can introduce some (small, < 1 kcal/mol) >> errors. Since the sum of the NOCV contributions 1 to 8 does give >> only -33.41 kcal/mol, there might be some other problems. >> Possibility 1: the integration grid is too coarse. >> Possibility 2: the basis set itself is not flexible enough. (Maybe >> the frozen core is too large) >> Possibility 3: sometimes the NOCV orbitals with "large" NOCV >> eigenvalues do not catch (very) diffuse charge flow. >> >> So, if you want to try to fill the gap, you could try to make the >> calculation a bit more accurate. (And hope it is not possiblity >> 3...there is no solution for that one) >> >> Greetings, >> Marc >> >> PS: Symmetry and NOCV might sound interesting but imho it is not. >> The NOCV combined with symmetry would then be applied to each sub >> space (for each irreducible representation) of the density matrix >> and one would not allow for charge flow between the irreducible >> representations.(which sometimes might be the case - one could argue >> about that) Without symmetry there is only one "sub" space which >> contains all the information. >> >> _______________________________________________ >> ADFlist mailing list >> ADFlist at scm.com >> http://lists.tofoba.com/mailman/listinfo/adflist -- dr Mariusz Mitoraj Department of Theoretical Chemistry Faculty of Chemistry, Jagiellonian University 30-060 Krakow, Ingardena 3 Poland
- 以前的消息（按线程）： [adf-list] Adflist Digest，第23卷，问题1
- 下一条消息（按线程）： [adf-list]帮助
- 消息排序： [ 日期 ] [ 线 ] [ 主题 ] [ 作者 ]