- Proposal title:
The information-entropy origins of molecular aromaticity
- Keywords (5):
Aromaticity, Information Entropy, Electron Delocalization, Chemical Reactivity, Excited States
- Applicant: Jagiellonian University in Cracow
- Principal investigator: dr Dariusz Wojciech Szczepanik
- Duration (in months): 60
- Number of team members: 6
- Budget (in PLN): 1 342 000
- Research field: Physical Sciences and Engineering (ST)
- Primary NCN Review Panel: Chemistry (ST4)
- Auxiliary NCN Review Panel: Theoretical and Computational Chemistry (ST4_004)
- Brief description of the project:
Aromatic rings in porphyrins and their naturally occurring derivatives are among the most important chemical individuals in the world: no aerobic life on this planet can do without the characteristic carbon- and nitrogen-based macrocycles, which carry oxygen in the bloodstream (as a part of hemoglobin) and allow plants to capture sunlight's energy with their chloroplasts. Over the last decades the exceptional electron-transport and energy-harnessing capabilities of the macro- and polycyclic aromatic species have been utilized in cancer therapy, drug delivery, bio-imaging, molecular electronics, solar cells, lighter converters, bio-sensors, quantum computing, photoluminescent materials, photodetectors, and many, many others, making aromaticity one of the most commonly exploited theoretical concepts in chemistry - according to the ISI Web of Science, in 2020 (until September) there were about 43 papers published every day that contained the word 'aromatic' (or its antithesis) in title, keywords or abstract. On the other hand, the lack of a rigorous definition and the resulting superfluous diversity (dozens of types and rules of aromaticity) and numerous examples of the discrepancies between different aromaticity criteria proposed in the literature, have become the main reasons for this concept being perceived by some members of the chemical community as an elusive, questionable and suspicious concept. But, if rightly?
In this project we propose a profound paradigmatic change of the concept of (anti)aromaticity, to reveal its true colors and unearth its real predictive power, with the following hypotheses: ① Chemical resonance underlying electron delocalization is essentially of information-entropic nature: the key effect of the interference of different resonance forms is that we lose information on the assignment of electrons to particular bonds; ② One of the most distinguished features of aromatic compounds is their capacity to counterbalance 'destructive' effects of the electron excitations on the ground-state system of π-conjugated bonds by redistribution of the resonance forms in such a way that maximizes the resonance-entropy production or at least minimizes the resonance-entropy loss to preserve as much information contained in their π-systems as possible.
In this context, the core objective of the project is to decipher information contained in the ground-state wavefunctions of selected topologically diversified aromatic molecules and underlying their unique physico-chemical properties, and to progress toward understanding of the first-principle rules that determine evolution of this information in the lowest-lying excited states, under the influence of external magnetic field as well as along chemical reactions.
All the research tasks in this project are organized in such a way that they enable validation of the project hypotheses gradually by providing answers to the following scientific questions:
(1) How to extract from the molecular wavefunction the information about assignments of electrons into particular bonds, and how to translate this information into the 'chemical language'?
(2) Is it possible to prove experimentally that the source of the chemical resonance is indeed of entropic nature?
(3) Why the currently used theoretical methods fail to provide a consistent and reliable description of the interplay between chemical resonance and the magnetic-response properties of the expanded porphyrins and PAHs?
(4) Is it possible to construct the lowest-lying excited singlet states from the ground-state wavefunction without explicit solving of the time-dependent Schrodinger equation, and what are the limits of the MIEP applicability?
(5) How can we use the resonance-entropy concept and MIEP in the design of emitters exhibiting thermally activated delayed fluorescence (TADF)
(6) and as a rationale for singlet fission chromophore design?
Thus, verification of project hypotheses requires cross-disciplinary approaches using knowledge from mathematics (probability and information theory), theoretical and computational chemistry, physics, and materials science, which makes it truly exciting multidisciplinary challenge. To make sure that all the key aspects of the project can be tackled within the foreseen time a team consisting of PI, 2 PhD and 3 MSc students will be composed. To guarantee the best expertise and resources available most of the research tasks will be carried out in close collaboration with the world-renowned experts (theoreticians and experimentalists) in the field of molecular aromaticity and materials science from China, USA, UK, Spain, and Sweden. All the research tasks in this proposal will be carried out with partial support of the PL-Grid Infrastructure (Poland), BSC-CNS (Spain), CSD3 (UK), and resources provided by Jagiellonian University and University of Girona. The most demanding high-level calculations will be performed using the purchased workstations with unique specifications. The state-of-the-art computational methods and experimental techniques will be used.
Validation of the maximum information-entropy principle for electronic transitions in aromatic molecules would potentially have far-reaching implications for predictive computational chemistry as well as organic chemistry in general. The results of the project will hopefully provide the basis for an updated and more comprehensive IUPAC definitions of the concepts of aromaticity (antiaromaticity), olefinicity, aliphaticity, etc. The project will also deliver a novel methodology, software tools and research-based knowledge that in the future could support the design of modern spin-bearing compounds, organic fields-effect transistors, resonance-driven optical-mechanistic switches, dye-lasers, solar collectors, and many others. A tangible result of the research project will be scientific papers published in reputed journals from the ISI Master Journal List.
- Assessment justification - strong points:
NCN Panel Expert #1:
(1) Very good project write-up! Especially the introduction is pleasant to read, as it introduced the topic from a general perspective that is accessible to a general chemist and positions the project in a broader context. This, surprisingly, does not happen often and the author should be commended for it.
(2) The project has potential to yield high-impact outcomes that may have general implications.
(3) I appreciate the presence of clear, logical figures especially in a theoretical/computational chemistry proposal.
(4) Research tasks - very well defined and formulated in appealing way, showing the PI has put much thought into the role of his future team members.
(5) Great prospective collaborations.
(6) A large proportion of star papers on the PI's CV, showing he is well capable of leading a project.
NCN Panel Expert #2:
(1) Highly fundamental research question which is relevant for many ongoing studies in chemistry.
(2) Potentially high impact project.
(3) Good description of project which couples real life experimental studies (from collaborators) with the fundamental theoretical studies proposed.
(4) Highly qualified 'junior' academic who clearly punches above his weight and is very active in the community.
(5) Very good track record of national and international grants with good output and impact.
(6) Excellent international integration of the team with collaborators in P.R. China, Spain, Sweden, UK, USA.
(7) Good team structure.
(8) Well reasoned budget.
External Reviewer #1:
(1) Highly innovative research proposal.
(2) The project is truly multidisciplinar.
(3) The originality of the proposed approach compared to the state-of-the-art in the field is convincingly discussed.
(4) Development and implementation of a new theoretical framework.
(5) The novel methodology and tools can have a cross-domain impact, with a large impact on the chemical community.
(6) Feasible in five-years.
(7) The professional profile of the PI is of high quality, and appropriate to support the ambitious objectives of the research proposal.
(8) International networking with renowned experts in the field.
External Reviewer #2:
(1) The research described is very challenging, but through collaborations there is some prospect for success in the task described that will push forward a field, i.e. understanding aromaticity, that has arguably stagnated for many decades with a focus on rules such as 4N+2 that describe the conditions for but do not fully rationalize the topic describe.
(2) The potential importance of developing a better understanding of processes such as singlet state fission and themally-activated delayed fluorescence from the standpoint of applications could be transformative in some contexts if new insights are successfully obtained.
External Reviewer #3:
(1) Very promising researcher with many publications.
(2) Applicant has experience in quantum chemical calculations required for project.
(3) Compelling idea with potential implications in chemistry and applications in photo and excited state chemistry.
(4) Can contribute to quantitative definition of aromaticity.
(5) Collaboration with experiments.
External Reviewer #4:
(1) The research project is original and innovative.
(2) The PI has found an original approach within the field of aromaticity, which has been extensively analyzed.
(3) The PI has the potential to establish his own research group.
(4) The PI demonstrates independent thinking and leadership qualities.
(5) The project is very ambitious and holds the promise to open new directions in the field of aromaticity.
(6) The PI is an expert in this field of research, almost all his papers in the last years are about this topic.
(7) The PI lacks still full international recognition, but this is reasonable taking into account the stage of his career. Besides, he has already published some original works on his own that have captured the attention of other reputed scientists in his field, with whom he is currently collaborating.
(8) The publication record of the PI has clearly improved over the last years, including lately relevant and high impact-factor publications.
(9) The project is well written, considers the risks a contingency plan where needed.
- Assessment justification - weak points:
NCN Panel Expert #1
(1) Reference 19 (ACIE, "to be submitted") and 23 (JACS "to be submitted") - this is a very bad practice and I strongly discourage the PI from doing this in his future grant applications as it is bound to do more harm than good. If the author intends to showcase the most recent research that has not been published in high-end journals, one idea is to post them on a preprint server and cite the DOI, but definitely not do it the way it has been done here. Response: Thank you for the comment and suggestion. FYI, reference 23 has eventually been published in Chemical Science
NCN Panel Expert #2
(1) The proposal lacks any argument for establishing the team and its composition. Response: Thank you for the comment. As a matter of fact, arguments for establishing the team and its composition can be found in the section "Objectives, Challenges, and Methodology" of the extended project description, and they were also briefly mentioned during the interview:
External Reviewer #1
(1) An elaborated risk analysis plan and a proposal for risk mitigation is lacking, in case that some objectives are not achieved. Response: Thank you for the comment. It was pointed out by External Reviewer #4 ("The project is well written, considers the risks a contingency plan where needed") that there are several places in the proposal where the risk analysis is performed and contingency plans are provided; e.g., at the end of the description of T.4: "Although the preliminary results (...) are very promising (...), this research task is classified as medium-risk because the presented strategy has not been fully validated. On one hand, if succeed it would have potentially far-reaching implications for predictive computational chemistry as well as organic chemistry in general. On the other hand, in the case of failure, execution of tasks T.5 and T.6 is not at risk since the electronic structures of most of the studied compounds will be determined also by utilizing traditional ab initio (TD-DFT and post-HF) calculations...". Nevertheless, I must admit that there might still be a room for the improvement of the description of the contingency plan to make it more clear; some details and explanations in this regard were given during the intervew
(2) The number of citations of the PI´s publications is relatively low, but this is probably due to the theoretical and methodological nature of his research. Response: That is true. Thank you for the comment.
(3) Missing some experimental collaborators to strengthen the impact of the computational and theoretical findings, especially for the more applied parts of the proposal. Response: It is really hard to response for this comment because in his detailed review the External Reviewer #1 did not provide any explanation for what he exactly means. Also, all the other experts and reviewers have found the collaboration with experimentalists a strong point of the proposal. In fact, the more applied part of the proposal (consisting of 3 separate research tasks) is going to be performed in close collaboration with experimentalists from Cambridge University (UK), Brookhheaven University (USA) and ExxonMobil (USA). This was clearly stated in the description of each the research task and in several other places in the proposal (including the one-page description in the section "INTERNATIONAL COOPERATION"); it was also emphasized during the interview:
External Reviewer #2
(1) I really struggle to come up with any obvious weaknesses and look forward to reading future publications from this group of collaborators to see if any new insight is provided that may guide my future research directions which are related to the rational design of novel molecular dyes such as porphyrins for applications. Response: Thank you for this comment.
External Reviewer #3
(1) Applicant not differentiated scientifically from former supervisors. Response: I cannot agree with that. FYI, I was formally supervised by Dr. hab. Janusz Mrozek (Jagiellonian University, Poland, in retirement) during my MSc (2008) and PhD studies (2011-2013). However, JM gave me a carte blanche from the very beginning to direct my research interests in mathematical chemistry and information theory in complete independence; among 16 joint papers with my supervisor, I am the first and the sole corresponding author in 14, and in all of those works I have brought up the original theoretical ideas myself (not to mention performing all the calculations and preparing the manuscripts). JM is not involved in this project and contributed nothing to its design.
(2) All tasks require involvement of past supervisor from Spain. Response: This is simply not true as Prof. Miquel Solà (Universitat de Girona, Spain) has never been my supervisor. We have been collaborating since 2016, but working independently - see my 2nd response to the NCN Panel decision in the next section as well as the statement of facts by Prof. Miquel Solà at the bottom of this site
(3) Moderate IF of publications. Response: Thank you for this comment. Actually, this is true but I would personally not consider this a weak point as about half of my papers consider different problems in mathematical chemistry and quantitative communication theory, and was published in highly specialized journals like the Journal of Mathematical Chemistry
(4) Lack of experience supervising students. Response: As a matter of fact, in my previous research projects I led the teams in which I have succesfully interacted with students and postdocs who are co-authors of my 18 publications. Also, to the best of my knowledge there is no formal requirement of being a supervisor of PhD students or have such an experience in the Sonata Bis call.
(5) Unbalanced team composition. Response: Please see my response to the comment by NCN Panel Expert #2.
(6) There is no contingency plan. Response: Please see my response to the comment (1) by External Reviewer #1.
(7) The project is not sufficiently separated from other funded projects of the applicant. Response: This project is not a continuation of any of my previous projects, since the concept of the "resonance-entropy" is used therein for the very first time as a basis for the original project hypotheses. This fact was emphasized several times during the interview, and it has been noticed by all the other experts and external reviewers who unanimously judged the project to be original and (highly) innovative. In his detailed review the External Reviewer #3 wrote: "The theme of this project is very interesting however the description does not sufficiently explain how it is different from other projects of the applicant which are already funded. [...] This is aggravated by the fact that several of the applicant's publications acknowledge funding from more than one of his grants." Thus, it seems that the reviewer checked meticulously the aknowledgements in publications that are the outcomes of my previous projects but did not find time to read the corresponding abstracts to see for himself that none of those works is in any relation to the current proposal, which, once again, for the very first time combines the sophisticated algebra of Shannons communication channels from Information Theory with the theory of chemical resonance and aromaticity.
(8) The project suggests dependence (not independence) of applicant from past supervisors. Response: I fully disagree with this comment as it is based on false premises - see my responses (1) and (2).
External Reviewer #4
(1) The project is perhaps too ambitious for a team of this size. The PI expects to produce 15-20 papers in five years, which is about half his production so far. Some tasks I believe will take much more time than it is currently planned. Response: Thank you for the comment. The estimation of 15-20 papers in 5 years is based on the fact that the outcome of my 3-years NCN Sonata IX project (involving PI and two co-investigators) was in total 15 publications, and the outcome of my 2-years MSCA project was a book chapter and 9 papers.
- Decision: Rejected by 2nd panel
/5.00) Novelty (2.50
/3.00) Impact (3.00
/3.00) Facility (2.00
/3.00) Achievements (3.75
/5.00) Grants (3.75
(1) The scientific aspects of the proposal are cutting edge and target an important fundamental problem. However, (2) it is not clear to what extent the proposed work will be original work by the applicant, as a former advisor is involved in all aspects of the proposed work (3) which is a straight continuation of earlier projects. (4) In its present form the project will not allow the applicant to reach full independence. (5) Aspects of the project and prior accomplishments are oversold and (6) the choice of experimental collaborators is not convincing.
(1) Thank you for this comment.
(2) I personally find it highly disrespectful that the NCN Expert Panel ignored the statement I gave during the interview that I am the sole author of this project proposal and all the ideas therein presented are exclusively my own, and no one else contributed toward the desing of all the research tasks! Below is a copy of the corresponding slide presented during the interview. Also, it has to be emphasized that Prof. Miquel Solà has never been my supervisor as repeatedly claimed by the External Reviewer #3; we have been collaborating for about 5 years, but working independently - even during my stay in MS's research group as a MSCA fellow, I was training members of his group in using the EDDB method and at the same time I was conducting my own research projects fully independently - see the "Statement of facts" by MS at the bottom of this site.
(3) I fully disagree with this statement. This project is not a continuation of any of my previous projects and this fact was emphasized several times during the interview
. In fact, only the External Reviewer #3 wrongfully and unduly claims that "the project is not sufficiently separated from other funded projects" without a shred of concrete evidence - see my response to the comment(7) by External Reviewer #3 - while all the other experts and reviewers claim the opposite and highlight every step of the way originality of the project proposal (e.g. "Highly innovative research proposal", "The originality of the proposed approach compared to the state-of-the-art in the field is convincingly discussed", "The research project is original and innovative", "The PI has found an original approach within the field of aromaticity, which has been extensively analyzed", "I judge the project to be innovative..."). Admittedly, in my previous projects I investigated different types of aromatic compounds using different methodologies, but neighter of them is connected in any way to the current proposal. Even if one assume that the word "aromatic" (and its declinations) makes the scientific projects somehow related to each other, please compare the titles of my previous projects (bold black) and the current proposal (bold red) with the ones by the Applicant who was awarded with Sonata Bis grant within the same call:
(4) I disagree with this comment completely - see my response to comment (8) by the External Reviewer #3 and the statement of facts by Prof. Miquel Solà at the bottom of this site.
(5) It is really hard for me to find a ground for the comment "Aspects of the project and prior accomplishments are oversold" in the experts/reviewers opinions. Also, it is not clear for me what was the basis for the score 3.75
/5.00 in evaluation of the execution of my previous grants since the official result of the evaluation o my previous NCN project (Sonata IX) was 100.00
/100.00 with the comment "The project has been realized exemplary!"
(6) This comment is based on the secluded opinion by the External Reviewer #1, which was not explained in the detailed review, and which clearly contradicts opinions by all the other experts and reviewers - see my response to the comment (3) by External Reviewer #1.
- Outcome of the Appeal:
- Statement of facts by Prof. Miquel Solà