Theoretical Chemistry Accounts Research Articles

Saying farewell and welcoming new leadership

quite favorably to this modus operandi. In addition, to accommodate authors who want more options with respect to Open Access publishing, TCA adopted and continues to adhere to a Green Open Access self-archiving model and a hybrid Gold Open Access publishing model. Another hallmark of TCA has been its commitment to the publication of feature articles by established and emerging leaders in the theoretical/computational field. We have worked with authors to ensure that the feature article style is very flexible—for example with regard to page length—with the goal of providing an overview of a model or of an area but with the key difference from feature articles in many other journals is that such articles in TCA may be directed to an audience of theoretical chemists rather than to a broader audience that may be less knowledgeable about theoretical concerns. I would be remiss in departing if I failed to express my gratitude to the many individuals whose contributions were seminal to the ongoing success of TCA during my own time as Editor. These include the publishing editors from Springer with whom I have worked, the production staff, my advisory and associate editors, members of the editorial board, and first and foremost, the authors and reviewers who have advanced our field through their scholarly contributions to TCA over the years. With the continued support of these many talented individuals, I am certain that TCA will maintain its preeminence under the leadership of Drs. Adamo and Ciofini, and I wish them all success moving forward. It has been a privilege to serve, since the year 2000, as the 4th Editor-in-Chief for theoretical chemistry accounts (TCA). Founded in 1962, TCA remains the oldest journal devoted exclusively to publishing developments and applications of theoretical chemistry. As a legacy of the prior Editors-in-Chief as well—Hermann Hartmann, Klaus Ruedenberg, and Don Truhlar—TCA continues to serve the broader Chemistry community with distinction. Mindful of that legacy, I believe that it is time to turn the reins of editorship over to a new pair of scholars particularly well suited to maintain TCA’s high standards while at the same time broadening its reach and the diversity of topics that it covers. I am delighted to announce that Carlo Adamo and Ilaria Ciofini have agreed to take on this responsibility, and I am confident that they will continue the journal’s commitment to excellence in service to the theoretical chemistry community. In my time as Editor-in-Chief, TCA launched a number of initiatives, including a switch to consecutive publishing, where all articles become published and can be cited immediately after the return of proofs. In recent years, we have also published a number of special collections, including a New Century issue (in Vol. 103, nos. 3–4, 2000, with perspectives on influential papers from the previous century) and a 50th anniversary issue (in Vol. 131, 2012, summarizing past accomplishments and offering thoughts about the future). Because of consecutive publishing, papers in such collections are not delayed by any need to await completion of the “slowest” contribution, and authors have responded

On the starting blocks

theoretical methods are necessarily entangled and a reference journal in this field, such as TCA, should in our opinion cover both aspects with the same intensity. We wish to follow the evolution of theoretical chemistry attracting, besides contributions from traditional theoretical chemists, also those from authors of communities straddling the borders of traditional disciplines. Particular care will be devoted to editorial initiatives that promote the achievements of young and emerging scientists. Of the many challenges we faced in science, accepting this joint editorial responsibility is clearly one of the most gratifying and permits us to assert that science, besides individuals, also rests on collaboration and constructive sharing. Indeed, conscious that a journal is made not only by its editorial board and staff, but also by its readers, authors and referees, we count on the active collaboration and initiative of all these partners, which we hope constantly to stimulate, being ready to support their proposals for new initiatives and activities. Please join us in continuing this bountiful adventure in theoretical chemistry called TCA. A new and exciting adventure will start for us in January 2015, that of serving as Editors-in-Chief for Theoretical Chemistry Accounts (TCA), a journal with a glorious history that has tracked the development of theoretical chemistry. Succeeding such prestigious Editors-in-Chief as Hermann Hartmann, Klaus Ruedenberg, Don Truhlar and Chris Cramer is an honour and a duty to which we will commit our best, counting on our complementary scientific attitudes and expertise. Especially thanks to the active and inventive leadership of Dr. Cramer, we inherit the editorship of a journal that is vital and proficient in fast publication of high-standard papers covering a wide variety of topics in theoretical chemistry. In line with Dr. Cramer’s editorship, we will continue to target excellence in science and efficiency in publication which are nowadays renowned as strong points of TCA. One of the main goals of our editorship will be to follow the rapid growth, witnessed especially in the last years, of emerging domains encompassed by theoretical chemistry including now biology, materials science and physics. In this context, the development and the application of

Changing of the guard for Theoretical Chemistry Accounts

Chris Cramer has perfectly guarded TCA through times of significant changes in the publishing environment. Milestones of these changes were the introduction of the OpenChoice option in 2004 to allow TCA authors to publish in full open access, the implementation of an online submission and peer-review system in 2007, a doubling of submissions since then, or the change to consecutive article publishing in 2012, the year of TCA’s 50th anniversary. This also includes the foundation of the “Highlights in Theoretical Chemistry” series together with Don Truhlar, which makes selected TCA topical collections available in book format for wider visibility. On behalf of Springer, I would like to thank Chris Cramer for all his achievements such as arranging for outstanding topical collections. Personally, I would like to thank him for a constructive and enjoyable collaboration over many years. I very much look forward to continuing this successful collaboration from next year onwards with Ilaria Ciofini and Carlo Adamo, both long-time authors and reviewers for TCA. Carlo Adamo has been one of the guest editors for the topical collection honoring Vincenzo Barone published 2012. While the new Editors-in-Chief certainly will bring in new perspectives, and are welcome to do so, all is set for continuing the tradition of a well-respected journal. Announcements such as the appointment of new Editorsin-Chief are usually made “with great pleasure”, and this is completely true for announcing that Ilaria Ciofini and Carlo Adamo (Ecole Nationale Superieure de Chimie de Paris, France) will start in that role beginning next year. However, certainly I cannot find any pleasure whatsoever in announcing at the same time that Chris Cramer will step down as Editor-in-Chief for Theoretical Chemistry Accounts at the end of this year. In such a situation of mixed feelings, it is reassuring to know that not only two competent and highly reputed scientists such as Ilaria Ciofini and Carlo Adamo have accepted the invitation to become Editor-in-Chief, but that Chris Cramer will continue to support the development of TCA as a member of the Editorial Board as well as continue to run @TheorChemAcc, the Twitter account of TCA initiated by him. Likewise and thankfully, Don Truhlar will continue as Chief Advisory Editor, and Weitao Yang as Associate Editor. To assure a smooth handover of responsibility, Ilaria Ciofini and Carlo Adamo will start as Associate Editors already in September 2014. Editors-in-Chief are the guards of scientific quality as well as of the reputation of their journal. So over the coming months, the TCA community in particular and all theoretical chemists in general can watch the changing of the guard for the oldest journal in the field!

Preface to the ESPA-2012 special issue

This issue of Theoretical Chemistry Accounts contains a recollection of some of the work presented and discussed at the 8th edition of the Electronic Structure: Principles and Applications (in short, ESPA-2012). The ESPA events are biennial international research conferences organized within the activities of the Spanish Theoretical Chemistry groups that co-organize the Interuniversity Doctorate in Theoretical Chemistry and Computational Modeling. The main aim behind all ESPA conferences, shared by the organizers of ESPA-2012, is promoting scientific excellence and exchange of ideas among their Ph. D. students, in a friendly environment. ESPA-2012 follows previous events held in Madrid, San Sebastia’n, Sevilla, Valladolid, Santiago de Compostela, Palma de Mallorca, and Oviedo.

From quantum mechanics to force fields: new methodologies for the classical simulation of complex systems

Molecular dynamics simulations have become one of the key methods for simulating the properties of biological systems and complex materials. Underlying such simulations are the force fields that describe how the energy varies as a function of geometry. As a result, the reliability of the simulations depends on the quality of the force field. In many cases, this requires the explicit incorporation of polarization. For these reasons, accurate electronic structure methods are playing an increasingly important role in the parameterization of force fields. This special issue of Theoretical Chemistry Accounts illustrates recent trends in the design and applications of accurate force fields. Of course, the field is vast and is growing rapidly; thus, we cannot claim completeness within such a collection. However, the following 15 papers reflect the present questions including the strategies for (i) the inclusion of the polarization energy and (ii) an optimal parametrization of model and highlight the directions to follow as new exciting fields of application emerge. Three papers discuss the optimization and parametrization of new models.

Computational modeling of extended systems

Advancements in computing architecture and in theoretical techniques allow for the modeling of complex, extended systems. This section of the 50th anniversary issue of Theoretical Chemistry Accounts highlights modeling work performed on nanostructured systems and underscores the enormous potential for synergy between theory and experiment in modern nanoscience.

Theoretical chemistry: current applications to photochemistry and thermochemistry

A historical perspective is given contrasting challenges and advances in theoretical chemistry at the time the first issue of Theoretical Chemistry Accounts appeared in 1962 and the progress achieved since then as expressed in current state-of-the-art applications in photochemistry and thermochemistry.

A Festschrift in honor of Akira Imamura’s 77th birthday, his recent retirement, and his many contributions to theoretical chemistry

The Imamura Festschrift Issue of Theoretical Chemistry Accounts is a special multifocus international issue commemorating the 77th birthday of Professor Akira Imamura and his many contributions to the fields of theoretical chemistry, polymer science, molecular biophysics, chemical physics, and molecular biology. This issue has contributions in theoretical developments of methods applicable to larger polymeric systems, for example, the elongation method pioneered by Professor Imamura and his group, and more recently by the groups of Professor Yuriko Aoki at Kyushu University and Professor Feng Long Gu at South China Normal University, supported by several funds from the Japan Science and Technology Agency (JST). In addition, there are contributions from top experimental and theoretical groups in the areas of nanotechnology, bionanotechnology, quantum transport theory, molecular biophysics, molecular electronics, and even molecular medicine and medical diagnostics, where the marriage between theory and experiment is very important to be able to fully understand, interpret, and utilize the wealth of new and exciting experimental data. The development of new and refined methods, and the extension of older more conventional methods, will be required for these fields to continue to evolve/co-evolve and develop, as they have in the last 60 years. But to evolve in a guided fashion (guided evolution), that is, to meet the needs and functions of not only the individual scientists and research groups but also of society in general, will require a concerted effort from not only experimentalists and theoreticians in each individual subdiscipline but also for them to work together and share their accumulated knowledge and experience, as is now being done in various research networks around the world, including the one originally initiated/formed by Professor Imamura and Professor Janos Ladik at the Third International Congress of Quantum Chemistry (ICQC) in Kyoto, Japan. Through this network, Professor Imamura has been able to pass on a wealth of knowledge, expertise, and experience to the current and future generations of scientists in Germany, the United States, and China, as Professor Imamura is still doing with his lectures both in Japan at Kyushu University and in China at South China Normal University, and previously in Erlangen at the University of Erlangen, in Heidelberg at the German Cancer Research Center (DKFZ) in Germany, and in Ithaca, New York at Cornell University in the United States. He has been a real example of the modern protean research scientist and professor who has continued to be in research and teaching, active well beyond the formerly set retirement age of 63 or 65 set by society. The idea that researchers and professors cannot be active in their 60s, 70s, and 80s has now also been shown to be a misconception that needs to be corrected at the funding and institutional levels. Too many very active, knowledgeable, and experienced researchers and professors have been forced to stand on the sidelines, while those who have replaced them have very little practical knowledge, expertise, and more importantly, life experience. A whole generation of young academics are being hired who have never worked a day in industry, never visited an industrial laboratory and/or research group, and hence are unable, (don’t know) and in many cases, unwilling to train and educate their students with the skills they need to not only work in industry but also to create new and exciting new industries. The idea that the large chemical and pharmaceutical companies and government laboartories will hire all of the ever increasing numbers of undergraduate and graduate (MSc and PhD) students no longer applies. The university mission is no longer just to teach, give knowledge, and to do research, but also to innovate, that is, to train the students to take their acquired knowledge from their text books and apply it with the newly acquired knowledge in the research laboratories to start and develop new industries and companies. But this means that the students need to be trained in the fields of engineering economics, finance, and scientific and international law, so that they are able to undertake such projects, in addition to understanding and applying their scientific knowledge. It will also require a concerted effort by funding agencies, state, local, federal, and even international bodies that seek to create and sustain strong economies and infrastructure, which will support and be supported by the highly motivated, trained, and educated work forces. The third pillar is now being established, but it needs to now be totally and completely integrated with the other establishments and infrastructure.

Theoretical and computational chemistry in Spain

1 PrefaceThe Ninth Congress of the World Association of Theoret-ical and Computational Chemists, one of the most importantscientific meetings focusing on Theoretical Chemistry, willtake place in Santiago de Compostela (Spain) in July 2011.The decision to celebrate this Congress in Spain representsan implicit recognition of the increasing role of the Spanishcommunity in this field. Indeed, this phenomenon hadalready been illustrated in several bibliometric studies thathad pointed out the amount and quality of Spanish theo-retical chemistry over the last 30 years [1]. With this asbackground, the Editor of Theoretical Chemistry Accounts,Christopher Cramer, proposed the coordination of a specialissue devoted to Theoretical Chemistry in Spain. We, theguest editors, have tried to assemble a collection of papersthat surveys a wide landscape of the various research linesthat are presently under study by investigatory teams spreadall over the nation.The current state of Spanish Theoretical Chemistry isbuilt upon a historical foundation developed by severalgenerations of professors and researchers, all of whom ele-vated the level of this discipline so as to occupy a prominentrole within both the Spanish Chemistry and the worldTheoretical Chemistry communities. The seeds of QuantumChemistry in Spain were introduced by the late ProfessorsJose´ Ignacio Ferna´ndez Alonso and Salvador Senent, in the1950s. Ferna´ndez Alonso was introduced to the disciplinefirst at the Centre de Chimie The`orique de France, workingwith Sandorfy, and later on at the California Institute ofTechnology, collaborating with Pauling. Senent was intro-duced to the field in the English School, at King’s Collegeand Oxford University, where he collaboratedwithCoulson.These two pioneers ofSpanish Quantum Chemistrybegan todevelop their research activity in this new discipline at theUniversities of Valencia, Valladolid and Auto´noma deMadrid. A significant number of young researchers wereinstructed in these two schools during the 1960s and 1970s.These individuals disseminated Quantum and TheoreticalChemistry to a large number of universities as they took upprofessorships primarily in Physical Chemistry.Parallel to this evolution within the academic environ-ment, the first quantum chemistry group in Barcelona wasfounded under the auspices of the Spanish Research Sci-entific Council (CSIC) by Santiago Olivella, who had beena collaborator with Dewar at the University of Texas.Similarly, at about the same time, Carmela Valdemoro andthe late Yves Smeyers started their activities at the InstitutoRocasolano in Madrid, and Joan Bertra´n began his studiesat the Centre de Meca´nique Ondulatoire in Paris, withDaudel as his Ph.D. supervisor. Bertran’s academicmobility over the course of his career contributed signifi-cantly to the wide dissemination of Quantum Chemistry inSpain and further contributed to the development of manyof the currently working teams in the field, particularly inCatalonia. Finally, Ramo´n Carbo´, first at the InstitutoQui´mico de Sarria´ and later at the University of Girona,was also a cornerstone for the development of TheoreticalChemistry in Catalonia.During the 1980s, a new generation of scientists, many ofthem the scientific progeny of the pioneers mentioned

Comments on the nature of the bonding in oxygenated dinuclear copper enzyme models

The nature of the bonding in model complexes of di-copper metalloenzymes has been analyzed by means of the electronic localization function (ELF) and by the quantum theory of atoms in molecules (QTAIM). The constrained space orbital variations (CSOV) approach has also been used. Density functional theory (DFT) and CASSCF calculations have been carried out on several models of tyrosinase such as the sole Cu 2 O 2 2 + central core, the Cu 2 O 2 ( NH 3 ) 6 2 + complex and the Cu 2 O 2 ( Imidazol ) 6 2 + complex. The influence on the central Cu 2O 2 moiety of both levels of calculation and ligand environment have been discussed. The distinct bonding modes have been characterized for the two major known structures: [Cu 2(μ–η 2: η 2–O 2)] 2+ and [Cu 2(μ–O 2)] 2+. Particular attention has been given to the analysis of the O–O and Cu–O bonds and the nature of the bonding modes has also been analyzed in terms of mesomeric structures. The ELF topological approach shows a significant conservation of the topology between the DFT and CASSCF approaches. Particularly, three-center Cu–O–Cu bonds are observed when the ligands are attached to the central core. At the DFT level, the importance of self interaction effects are emphasized. Although, the DFT approach does not appear to be suitable for the computation of the electronic structure of the isolated Cu 2O 2 central core, competitive self interaction mechanisms lead to an imperfect but acceptable model when using imidazol ligands. Our results confirm to a certain extent the observations of [M.F. Rode, H.J. Werner, Theoretical Chemistry Accounts 4–5 (2005) 247.] who found a qualitative agreement between B3LYP and localized MRCI calculations when dealing with the Cu 2O 2 central core with six ammonia ligands.

A comment on “Accurate ab initio determination of binding energies for rare-gas dimers by basis set extrapolation”

In this work we comment on an extrapolation scheme presented by Lee in Theoretical Chemistry Accounts, which is based on an extrapolation of energy differences instead of actual energies. In particular, we show that a very similar scheme had been introduced already in 1999, and used to estimate the MP5, CCSDT and FCI complete basis set limits of He2.

RETRACTED: Table of periodic properties of fullerenes based on structural parameters

The Editors would like to announce that the above article has been retracted. Reason: A paper by the same author, containing essentially the same data and conclusions, was published previously in Theoretical Chemistry Accounts 110 (6), 371–376, 2003 and again in Journal of Chemical Information and Computer Sciences 44 (1), 60–67, 2004.

Table of Periodic Properties of Fullerenes Based on Structural Parameters.

Abstract The Editors would like to announce that the above article has been retracted. Reason: A paper by the same author, containing essentially the same data and conclusions, was published previously in Theoretical Chemistry Accounts 110 (6), 371–376, 2003 and again in Journal of Chemical Information and Computer Sciences 44 (1), 60–67, 2004.

Addendum to “Gaussian-3 and related methods for accuratethermochemistry,” L.A. Curtiss, K. Raghavachari (2002) Theoretical Chemistry Accounts 108:61–70

Addendum to “Gaussian-3 and related methods for accuratethermochemistry,” L.A. Curtiss, K. Raghavachari (2002) Theoretical Chemistry Accounts 108:61–70

Introduction to the ECCC8 Proceedings Issue of Theoretical Chemistry Accounts

Introduction to the ECCC8 Proceedings Issue of Theoretical Chemistry Accounts

Bader's interatomic surfaces are unique

In this work we comment on the statement about the nonuniqueness of the solution of Bader's equation for defining atoms in molecules reported in the article of P. Cassam-Chenai and D. Jayatilaka in Theoretical Chemistry Accounts (2001) 105: 213–218

New challenges in quantum chemistry: Quests for accurate calculations for large molecular systems.

As quantum chemistry plays a more and more central role in many complicated chemical problems, it has become necessary to obtain accurate results for large molecular systems. Conventional quantum chemistry methods are either too expensive to apply to large systems or too approximate for the results to be reliable, and they fail to satisfy this requirement. A variety of different approaches is being developed with the aim of achieving this goal: local correlation methods; divide-and-conquer methods; linear-scaling density functional methods based on the fast multipole and other approximations; effective potential methods; and hybrid methods. ONIOM (our N-layered integrated molecular orbital plus molecular mechanics method), developed by the authors, is a hybrid method in which a large molecular system is divided into onion-skin-like layers, and different quantum chemistry/molecular mechanics methods are used for different parts of the system; the results are combined to extrapolatively estimate the results of high-level calculation for the real system. Several applications of ONIOM will be discussed.

Computer simulation studies of the structure and dynamics of ions and non–polar solutes in water

The mobility of simple ions such as alkali–metal and halide ions at room temperature shows two anomalies. Firstly, there are maxima in mobilities as a function of ion size for both positive and negative ions and, secondly, the maximum for negative ions occurs at a larger ionic radius than the maximum for positive ions. Theoretical treatments of this problem are reviewed and it is concluded that a molecular treatment of the system is needed to understand the results. Computer simulation using the simple point charge model (SPC/E) for water reproduced the observations and is used to discuss the application of theories. In particular, the nature of the first solvation shell is correlated with ion mobility. Simulation reveals a further anomaly, namely that if the charge is removed from a large ion, then it moves more slowly. This is interpreted as the result of formation of a solvent cage around the hydrophobic solute. The changes in local structure resulting from changes in charge and size also affect the solvation thermodynamics. Simulations show that the solvation entropy has a double maximum when viewed as a function of charge. The local minimum near zero charge is interpreted as being due to hydrophobic order, and the maxima as the result of structure breaking. This double maximum in the entropy of solvation is a signature of the hydrophobic cage effect. Comparisons are made between ion mobilities in liquid water at ambient and supercritical conditions.

Quantum computation, entanglement and state reduction

Some general foundational issues of quantum mechanics are considered and are related to aspects of quantum computation. The importance of quantum entanglement and quantum information is discussed a...

Direct effects of prostaglandin on renal function and renin release in anesthetized dog.

Direct effects of prostaglandin on renal function and renin release in anesthetized dog.