1,721,173 research outputs found
HFLD: A Nonempirical London Dispersion-Corrected Hartree-Fock Method for the Quantification and Analysis of Noncovalent Interaction Energies of Large Molecular Systems †
No full textA nonempirical quantum mechanical method for the efficient and accurate quantification and analysis of intermolecular interactions is presented and tested on existing benchmark sets. The leading idea here is to focus on the intermolecular part of the correlation energy that contains the all-important London dispersion (LD) interaction. To keep the cost of the method low, essentially at the level of a Hartree-Fock (HF) calculation, the intramolecular part of the correlation energy is neglected. We also neglect the nondispersive parts of the intermolecular correlation energy. This scheme that we denote as Hartree-Fock plus London dispersion (HFLD) can be readily realized on the basis of the recently reported multilevel implementation of the domain-based local pair natural orbital coupled-cluster (DLPNO-CC) theory in conjunction with the well-established local energy decomposition (LED) analysis. The accuracy and efficiency of the HFLD method are evaluated on rare gas dimers, on the S66 and L7 benchmark sets of noncovalent interactions, and on an additional set (LP14) consisting of bulky Lewis pairs held together by intermolecular interactions of various strengths, with interaction energies ranging from -8 to -107 kcal/mol. It is first shown that the LD energy calculated with this approach is essentially identical to that obtained from the full DLPNO-CCSD(T)/LED calculation, with a mean absolute error of 0.2 kcal/mol on the S66 benchmark set. Moreover, in terms of the overall interaction energies, the HFLD method shows an efficiency that is comparable to that of the HF method, while retaining an accuracy between that of the DLPNO-CCSD and DLPNO-CCSD(T) schemes. Since the underlying DLPNO-CCSD method is linear scaling with respect to the system size, the HFLD approach also does not lead to new bottlenecks for large systems. As an illustrative example of its efficiency, the HFLD scheme was applied to the interaction between the substrate and the residues in the active site of the cyclohexanone monooxygenase enzyme. The excellent cost/performance ratio indicates that the HFLD method opens new avenues for the accurate calculation and analysis of noncovalent interaction energies in large molecular systems
Effect of Electron Correlation on Intermolecular Interactions: A Pair Natural Orbitals Coupled Cluster Based Local Energy Decomposition Study
No full textThe development of post-Hartree-Fock (post-HF) energy decomposition schemes that are able to decompose the HF and correlation components of the interaction energy into chemically meaningful contributions is a very active field of research. One of the challenges is to provide a clear-cut quantification to the elusive London dispersion component of the intermolecular interaction. London dispersion is well-known to be a pure correlation effect, and as such it is not properly described by mean field theories. In this context, we have recently developed the local energy decomposition (LED) analysis, which provides a chemically meaningful decomposition of the interaction energy between two or more fragments computed at the domain-based local pair natural orbitals coupled cluster (DLPNO-CCSD(T)) level of theory. In this work, this scheme is used in conjunction with other interpretation tools to study a series of molecular adducts held together by intermolecular interactions of different natures. The HF and correlation components of the interaction energy are thus decomposed into a series of chemically meaningful contributions. Emphasis is placed on discussing the physical effects associated with the inclusion of electron correlation. It is found that four distinct physical effects can contribute to the magnitude of the correlation part of intermolecular binding energies (Eint C ): (i) London dispersion, (ii) the correlation correction to the reference induction energy, (iii) the correlation correction to the electron sharing process, and (iv) the correlation correction to the permanent electrostatics. As expected, the largest contribution to the correlation binding energy of neutral, apolar molecules is London dispersion, as in the argon dimer case. In contrast, the correction for the HF induction energy dominates Eint C in systems in which an apolar molecule interacts with charged or strongly polar species, as in Ar-Li + . This effect has its origin in the systematic underestimation of polarizabilities at the HF level of theory. For similar reasons, electron sharing largely contributes to the correlation binding energy of covalently bound molecules, as in the beryllium dimer case. Finally, the correction for HF permanent electrostatics significantly contributes to Eint C in molecules with strong dipoles, such as water and hydrogen fluoride dimers. This effect originates from the characteristic overestimation of dipole moments at the HF level of theory, leading in some cases to positive Eint C values. Our results are apparently in contrast to the widely accepted view that Eint C is typically dominated by London dispersion, at least, in the strongly interacting region. Clearly, post-HF energy decomposition schemes are very powerful tools to analyze, categorize, and understand the various contributions to the intermolecular interaction energy. Hopefully, this will eventually lead to insights that are helpful in designing systems with tailored properties. All analysis tools presented in this work will be available free of charge in the next release of the ORCA program package
Open-Shell Variant of the London Dispersion-Corrected Hartree-Fock Method (HFLD) for the Quantification and Analysis of Noncovalent Interaction Energies
No full textThe London dispersion (LD)-corrected Hartree-Fock (HF) method (HFLD) is an ab initio approach for the quantification and analysis of noncovalent interactions (NCIs) in large systems that is based on the domain-based local pair natural orbital coupled-cluster (DLPNO-CC) theory. In the original HFLD paper, we discussed the implementation, accuracy, and efficiency of its closed-shell variant. Herein, an extension of this method to open-shell molecular systems is presented. Its accuracy is tested on challenging benchmark sets for NCIs, using CCSD(T) energies at the estimated complete basis set limit as reference. The HFLD scheme was found to be as accurate as the best-performing dispersion-corrected exchange-correlation functionals, while being nonempirical and equally efficient. In addition, it can be combined with the well-established local energy decomposition (LED) for the analysis of NCIs, thus yielding additional physical insights
Local energy decomposition analysis of hydrogen-bonded dimers within a domain-based pair natural orbital coupled cluster study
No full textThe local energy decomposition (LED) analysis allows for a decomposition of the accurate domain-based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] energy into physically meaningful contributions including geometric and electronic preparation, electrostatic interaction, interfragment exchange, dynamic charge polarization, and London dispersion terms. Herein, this technique is employed in the study of hydrogen-bonding interactions in a series of conformers of water and hydrogen fluoride dimers. Initially, DLPNO-CCSD(T) dissociation energies for the most stable conformers are computed and compared with available experimental data. Afterwards, the decay of the LED terms with the intermolecular distance (r) is discussed and results are compared with the ones obtained from the popular symmetry adapted perturbation theory (SAPT). It is found that, as expected, electrostatic contributions slowly decay for increasing r and dominate the interaction energies in the long range. London dispersion contributions decay as expected, as r−6. They significantly affect the depths of the potential wells. The interfragment exchange provides a further stabilizing contribution that decays exponentially with the intermolecular distance. This information is used to rationalize the trend of stability of various conformers of the water and hydrogen fluoride dimers
Extrapolation to the Limit of a Complete Pair Natural Orbital Space in Local Coupled-Cluster Calculations
No full textThe domain-based local pair natural orbital (PNO) coupled-cluster DLPNO-CCSD(T) method allows one to perform single point energy calculations for systems with hundreds of atoms while retaining essentially the accuracy of its canonical counterpart, with errors that are typically smaller than 1 kcal/mol for relative energies. Crucial to the accuracy and efficiency of the method is a proper definition of the virtual space in which the coupled-cluster equations are solved, which is spanned by a highly compact set of pair natural orbitals (PNOs) that are specific for each electron pair. The dimension of the PNO space is controlled by the TCutPNO threshold: only PNOs with an occupation number greater than TCutPNO are included in the correlation space of a given electron pair, whilst the remaining PNOs are discarded. To keep the error of the method small, a conservative TCutPNO value is used in standard DLPNO-CCSD(T) calculations. This often leads to unnecessarily large PNO spaces, which limits the efficiency of the method. Herein, we introduce a new computational strategy to approach the complete PNO space limit (for a given basis set) that consists in extrapolating the results obtained with different TCutPNO values. The method is validated on the GMTKN55 set using canonical CCSD(T) data as the reference. Our results demonstrate that a simple two-point extrapolation scheme can be used to significantly increase the efficiency and accuracy of DLPNO-CCSD(T) calculations, thus extending the range of applicability of the technique
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Local energy decomposition of coupled‐cluster interaction energies: Interpretation, benchmarks, and comparison with symmetry‐adapted perturbation theory
No full textLocal energy decomposition analysis provides a breakdown of the domain‐based local pair natural orbital CCSD(T) [DLPNO‐CCSD(T)] energy into additive contributions representing the interaction between pairs of user‐defined fragments. Each of these fragment‐pairwise components can be further decomposed into a sum of physically meaningful terms, such as electrostatics, dispersion, and exchange. In this study, the dependence of such energy terms on the basis set size, the approximations used for the two‐electron integrals, and the localization scheme used for the virtual orbitals have been carefully evaluated on the interaction energies of the S66 benchmark set. A comparison with the energy components obtained at the SAPT2 + (3)δMP2 level of Symmetry‐Adapted Perturbation Theory is also provided
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
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