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wanlaifengji

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[资源] 一篇要求Major Revision的文章的修改

前段时间投了国外一期刊一篇文章,意见让Major Revision(见下). 看了意见,第一印象是比较难对付, 于是稍微放了放, 考虑了一天(基本上一天中的空闲时间都在想), 作了修改(修改信见下), 上传修改稿,隔一天后编辑来信接受.
审稿意见:
Recommendation: Major Revision
Comment: The authors have calculated the potential energy curves (PECs) of the lowest three electronic states of the AAA system by multi-reference electronic structure methods.Geometries of all stationary points along the PECs were optimized at the CASPT2/cc-pVQZ level.Geometry scans for the bbb angle were also performed at the CASPT2/cc-pVQZ//CASSCF/ANO level.
It was found that the calculated geometries were not largely different from those of previous work at the CASSCF/cc-pVQZ level (their reference [3]). The relative energies of the stationally points were also predicted similarly to previous results at the ICMRCI/cc-pVQZ level [3]. It is noted that the CASPT2/cc-pVQZ level the authors employed is not necessarily more accurate than the ICMRCI/cc-pVQZ model used in reference [3] (Although geometries were optimized at the lower CASSCF/cc-pVQZ level in [3]). Therefore, most of the results presented here are of minor importance over previously-reported ones.
A new finding is the identification of the linear A2Π state as a saddle point by means of CASPT2 and DFT frequency calculations, in contrast to previous reports which located it as the minimum. A new bending minimum structure M1 is predicted as the true minimum on the 2A”' surface. These findings might inspire new experimental/theoretical studies, which make the present manuscript worth being published.
However, the linear ccc and the bending M1 structures are approximately isoenergitic apart by only 0.05 eV, the former state being electronically 2-fold degenerate. In treating such a subtle problem, the authors should make more efforts to justify their theoretical treatment:
(1) The authors should clarify how to obtain the CASSCF orbitals for three electronic states, 12A’,12A”, and 22A’. Is it state-averaged or optimized independently for each state? It seems important especially for the degenerate Π states.
(2) The employed CASPT2/cc-pVQZ level being not definitively accurate, results obtained here should be compared carefully with previous experimental or theoretical data for accuracy checking. Table 1 is not enough. Calculated PECs can be used to predict the Infrared spectra reported in [2], for example.
Therefore, the referee recommends the publication of the manuscript after the authors address the above issues.
修改回信(客套话免了):
Responds to the Referee’s reviews:
1. Response to comment (1): (The authors should clarify how to obtain the CASSCF orbitals for three electronic states……)
In our CAS calculations, we did not use the so-called state-average technique.  Considering the Reviewer’s suggestion, we added one sentence “For each state, the optimization was performed independently.” in section “Computational Details” (On Page 2, the third paragraph, line 5)

2.  Response to comment (2): (The employed CASPT2/cc-pVQZ level being not definitively accurate……):
We understand the Reviewer’s suggestions. However, we consider that the designed accuracy checking on the method is not necessary. It is known that the CASPT2 and CASSCF methods are effective for theoretical studies of excited electronic states of molecules and molecular ions (For examples, J. Phys. Chem. A 2004, nnn; J. Chem. Phys. 2004, nnn; J. Phys. Chem. A 2006, nnn; ChemPhyschem 2009, nnn, etc.). We think for such system the basis set cc-pVQZ is sufficient. In the manuscript we compared our results with the previous theoretical data (from Ref.[3], we believed that the data in Ref.[3] should be the most accurate in all the previous data). However, we did not compare our results with the previous experimental data. The reason is following: only the frequencies of the ground state of AAA had been reported (in Ref.[2]) and no other experimental data were available. In Ref.[2], the frequencies of AAA had been calculated at the CASSCF/cc-pVDZ level. The calculated frequencies are near to the experimental. In fact we also carried out CASSCF frequency calculations and found our calculated results are similar with those in Ref.[2]. We do not think the compare of the frequency is necessary. Without the comparing would not influence the conclusions of the present manuscript. Considering the Reviewer’s suggestion, we added the B3LYP/cc-pVTZ calculated results in Table I and made some changes (see following). We believe the DFT calculated results are helpful in understanding the conclusions.
Some changes:
a): The Table I were revised.
b): on Page 3, in the third paragaphy the last sentence “Therefore, we will not report the B3LYP optimized geometries in present paper.” was deleted.
c): in the first paragaphy of Section “Results and Discussion”, some sentences “The DFT calculated results are also listed in Table I. For the DFT calculated results were similar with the CASPT2 results, in the text we will mainly report the CASPT2 resulsts.” were added (on Page 3).

3. We tried our best to improve the manuscript and made some changes in the manuscript.  These changes will not influence the content and framework of the paper. And here we did not list the changes.

[ Last edited by wanlaifengji on 2009-7-13 at 23:37 ]

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