International Journal of Quantum Chemistry

Cover image for Vol. 118 Issue 8

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 2.92

ISI Journal Citation Reports © Ranking: 2016: 12/100 (Mathematics Interdisciplinary Applications); 12/36 (Physics Atomic Molecular & Chemical); 59/146 (Chemistry Physical)

Online ISSN: 1097-461X

Associated Title(s): Journal of Computational Chemistry


    1. Off-center Gaussian functions: Applications toward larger basis sets, post-second-order correlation treatment, and truncated virtual orbital space in investigations of noncovalent interactions

      Miroslav Melicherčík, Denisa Suchá, Pavel Neogrády and Michal Pitoňák

      Version of Record online: 19 FEB 2018 | DOI: 10.1002/qua.25580

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      A grid of s-type Gaussians surrounding the molecule is intended to substitute for the presence of diffuse basis functions. Diffuse basis function are important for the accurate description of noncovalent interactions, but linear dependency issues in the atomic orbital often cause convergence problems. An s-functions grid place on the surface of the molecule allows more favorable scaling of the total number of basis functions with the molecular size to be achieved.

    2. Toward an universal quantum QSPR operator

      Ramon Carbó-Dorca

      Version of Record online: 19 FEB 2018 | DOI: 10.1002/qua.25602

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      The thermal voltage concept, which has been used for a long time in solid state lore, is employed to develop a general formalism, tending to provide the so-called quantitative structure–properties relations from a quantum theoretical point of view. In this way, thermal voltage permits first to define a homothetic scaling of quantum electronic density functions. Three application examples in the domain of chirality, toxicity, and biological activity are provided. Original Drawing by Pep Camps (Painter from Girona).


    1. The ability of Ex2Box4+ to interact with guests containing π-electron-rich and π-electron-poor moieties

      Glaucio R. Nagurniak, Giovanni F. Caramori, Alvaro Muñoz-Castro, Renato L. T. Parreira and Éder H. da Silva

      Version of Record online: 16 FEB 2018 | DOI: 10.1002/qua.25607

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      ExBox4+ is able to trap guests containing both π-electron rich and π-electron poor moieties. The results point strictly to host–guest interactions are mainly noncovalent (dispersion) and no significant charge-transfer is observed.

    2. Silicon buckyballs versus prismanes: Influence of spatial confinement on the structural properties and optical spectra of the Si18H12 and Si19H12 clusters

      Mark V. Gordeychuk, Konstantin P. Katin, Konstantin S. Grishakov and Mikhail M. Maslov

      Version of Record online: 16 FEB 2018 | DOI: 10.1002/qua.25609

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      A genetic algorithm is combined with density functional theory to predict how cylindrical spatial confinement affects the structural characteristics and optical adsorption spectra of the low-energy Si18H12 and Si19H12 isomers. The ground states of these clusters are almost spherical buckyballs rather than earlier predicted aromatic structures constructed from Si20H20 dodecahedrane. If the clusters are under cylindrical spatial constrains, their ground states are oblong cages rather than prismanes.


    1. Predicting the primary fragments in mass spectrometry using ab initio Roby–Gould bond indices

      Khidhir Alhameedi, Björn Bohman, Amir Karton and Dylan Jayatilaka

      Version of Record online: 14 FEB 2018 | DOI: 10.1002/qua.25603

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      There is currently a scarcity of computational methods supporting the elucidation of unknown compounds by mass spectrometry. The highest intensity peak (base peak) in electron impact mass spectrometry can be predicted correctly for 65 out of 75 test molecules using the a newly developed protocol in which Roby–Gould bond indices are applied to ground state and cation ab initio wavefunctions.

    2. Binding maps for the study and prediction of bimetallic catalyst surface reactions: The case of methanol oxidation

      Eoghan L. Gormley and Robert F. Berger

      Version of Record online: 14 FEB 2018 | DOI: 10.1002/qua.25606

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      Focusing on the competing pathways of methanol oxidation on platinum and platinum/gold bimetallic catalysts, this article explores a novel density functional theory (DFT)-based approach to the study of reactions on catalyst surfaces. In this approach, maps are constructed showing the binding energies of relevant atoms and molecules at all sites on a surface, which merges the computational simplicity and intuitive clarity of binding energy calculations with the site sensitivity of transition state calculations.

    3. The Liu-Parr power series expansion of the Pauli kinetic energy functional with the incorporation of shell-inducing traits: Atoms

      Eduardo V. Ludeña, Edison X. Salazar, Mauricio H. Cornejo, Darío E. Arroyo and Valentin V. Karasiev

      Version of Record online: 13 FEB 2018 | DOI: 10.1002/qua.25601

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      The effect of a shell-by-shell optimization of the expansion coefficients of the Liu-Parr expansion of the Pauli kinetic energy functional leads to striking improvements in the mean absolute error of the non-interacting kinetic energy functional. The results are the most accurate ones obtained to date for the representation of the non-interacting kinetic energy functional.

    4. Thermodynamic properties of diatomic molecule systems under SO(2,1)-anharmonic Eckart potential

      Gabriel Valencia-Ortega and Luis-Antonio Arias-Hernandez

      Version of Record online: 12 FEB 2018 | DOI: 10.1002/qua.25589

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      Diatomic molecules are good microscopic examples used to describe the thermodynamic behavior of several systems with a well-known basic structure and can also be considered as a bridge for the study and characterization of systems made up by more complex molecules. The present article takes into account the SO(2, 1)-anharmonic contribution in its energy spectrum. A set of thermodynamic functions can be compared for two types of molecular interaction with exact solutions.


    1. Information-entropic measures in free and confined hydrogen atom

      Neetik Mukherjee and Amlan K. Roy

      Version of Record online: 10 FEB 2018 | DOI: 10.1002/qua.25596

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      Rényi, Shannon, Tsallis entropy, Fisher information, and Onicescu energy in conjugate spaces have been reported for a confined Hydrogen atom embedded inside a spherical cavity. The effect of confinement is followed in an arbitrary state. It is found to be more prominent on higher- inline image states. At small cavity radius, all these measures behave in stark contrast to that found in free Hydrogen atom. Exact analytical results are offered for the circular states in free H atom.

    2. Explicitly correlated variational estimates of the energy levels of negative hydrogen ion under spatial confinement

      Reet Chandra, Bibhas Dutta, Jayanta K. Saha, Sukhamoy Bhattacharyya and Tapan K. Mukherjee

      Version of Record online: 7 FEB 2018 | DOI: 10.1002/qua.25597

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      Energy values of negative hydrogen ion within an impenetrable confinement are estimated in the framework of Ritz variational method using explicitly correlated Hylleraas-type basis set consistent with finite boundary condition. Although the singly excited states do not exist for a free negative hydrogen ion, well converged energy values of such states have been found within confinement and level crossings between two such states have been observed. The thermodynamic pressure felt by the ion inside the sphere is also estimated. Transformations of bound energy levels to quasi-bound states are reported.

    3. Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn-Resta approach

      Andrey A. Astakhov and Vladimir G. Tsirelson

      Version of Record online: 7 FEB 2018 | DOI: 10.1002/qua.25600

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      The electron organization of many-electron systems is considered in a context of the linear response theory extending the Kohn-Resta view on electron localization phenomenon. The variances of the local electronic position/momentum operators are linked via the fluctuation-dissipation theorem to the optical conductivity tensor, i.e. to observable spectroscopic properties. These variances, being related to quantum weak values, satisfy the extended uncertainty relation and quantify a degree of electron delocalization/localization in each point of a real space.

    4. Single- and double-electron reductions of CO2 by using superalkalis: An ab initio study

      Ambrish Kumar Srivastava

      Version of Record online: 7 FEB 2018 | DOI: 10.1002/qua.25598

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      The study demonstrates the use of superalkalis for single-electron reduction of CO2. For the first time using MP2, the interaction of CO2 with FLi2, OLi3, NLi4 superalkalis is modeled. The calculations suggest that these superalkalis are capable to reduce, that is, activate CO2. It has been also pointed that smaller superalkali performs better than larger ones in CO2 activation. Furthermore, CO2 can also be reduced to inline image by using superalkalis and excess electron.

    5. A computational investigation of the sulphuric acid-catalysed 1,4-hydrogen transfer in higher Criegee intermediates

      Farzaneh Sarrami, Felix A. Mackenzie-Rae and Amir Karton

      Version of Record online: 7 FEB 2018 | DOI: 10.1002/qua.25599

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      Criegee intermediates (CIs) are formed during the ozonolysis of unsaturated hydrocarbons in the troposphere. Ab initio modeling suggests that H2SO4 is an exceptionally effective catalyst for the 1,4 hydrogen shift reaction in CIs, leading to submerged reaction barrier heights relative to the free reactants and very low barrier heights relative to the reactant complexes. These findings have significant consequences for current atmospheric chemical models for regions of high sulphur concentrations.


    1. An orbital localization criterion based on the topological analysis of the electron localization function at correlated level

      Diego R. Alcoba, Ofelia B. Oña, Alicia Torre, Luis Lain and William Tiznado

      Version of Record online: 6 FEB 2018 | DOI: 10.1002/qua.25588

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      The decomposition of the overlap matrix according to the partitioning of the three dimensional physical spaces into basins provided by the electron localization function allow to define a localization index to be maximized using isopycnic orbital transformations. This procedure can be used to analyze the influence of the correlated and uncorrelated treatments on the orbital localization.

    2. Study of hydrogen bond dynamics in Nylon 6 crystals using IR spectroscopy and molecular dynamics focusing on the differences between α and γ crystal forms

      Mateusz Z. Brela, Marek J. Wójcik, Marek Boczar, Erika Onishi, Harumi Sato, Takahito Nakajima and Yukihiro Ozaki

      Version of Record online: 5 FEB 2018 | DOI: 10.1002/qua.25595

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      By solving the Schrödinger equation for proton potentials based on the snapshots extracted from ab initio MD, it is possible to explain the red shift in the IR spectra of the N[BOND]H stretching band observed in the γ form compared with the α form of Nylon 6. The HBs in the γ form are stronger than in the α form. This is mainly due to the dynamic effects.


    1. Studies on neuraminidase inhibition

      Pedro Paiva, Inês P. D. Costa, Cleide E. Ferreira, Pedro Ferreira, Andreia T. Pereira, Nuno M. F. S. A. Cerqueira, Pedro A. Fernandes and Maria J. Ramos

      Version of Record online: 2 FEB 2018 | DOI: 10.1002/qua.25592

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      Influenza virus infections account for significant morbidity and healthcare expenditures worldwide. Several influenza virus inhibitors are known to act through the inhibition of neuraminidase, a glycoprotein crucial for the infection of new host cells. Using molecular docking simulations, this work analyzes the chemical and structural features of 236 known neuraminidase inhibitors. The conclusion gathered in this study incites future rational design campaigns of new and more efficient drugs to fight the influenza virus.

    2. Water adsorption on the surface of Ni- and Co-based layer-structured cathode materials for lithium-ion batteries

      Yongseon Kim

      Version of Record online: 2 FEB 2018 | DOI: 10.1002/qua.25591

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      Ni-based layer-structured cathode materials are more vulnerable to moisture than conventional LiCoO2 cathodes in lithium-ion batteries. This study investigates the moisture adsorption mechanism on the surface of layer-structured cathodes, by comparing the behavior of water molecules on LiCoO2 and LiNiO2 surfaces. The structural and chemical changes during the adsorption process are analyzed by first-principles methods.

    3. Perturbed structures generated using coordinates derived from compliance constants in internal vibrations for QTAIM dual functional analysis: Intrinsic dynamic nature of interactions

      Waro Nakanishi and Satoko Hayashi

      Version of Record online: 2 FEB 2018 | DOI: 10.1002/qua.25590

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      A new method, called CIV, is proposed to generate perturbed structures for the quantum theory of atoms-in-molecules dual functional analysis; CIV employs coordinates for the internal vibrations (from which the CIV acronyms is derived) corresponding to the compliance constants. The dynamic nature of interactions based the perturbed structures with CIV is described as the “intrinsic dynamic nature of interactions,” since they are invariant to the choice of coordinate system.


    1. Lower scaling approximation to EOM-CCSD: A critical assessment of the ionization problem

      Achintya Kumar Dutta, Nayana Vaval and Sourav Pal

      Version of Record online: 1 FEB 2018 | DOI: 10.1002/qua.25594

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      None of the lower scaling approximations to equation of motion coupled cluster, EOMIP-CCSD, yields a consistent accuracy for outer valence, inner valence, and core-ionized states. EOMIP-CCSD(2)* has the best performance among all the approximate variants to EOMIP-CCSD, but at the highest computational cost. EOMIP-CCSD itself performs badly for core-ionized states, which are dominated by orbital relaxation effects. Even EOMIP-CCSDT fails to give quantitative accuracy for core ionization.


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      Multiscale modeling of enzymes: QM-cluster, QM/MM, and QM/MM/MD: A tutorial review

      Shideh Ahmadi, Lizandra Barrios Herrera, Morteza Chehelamirani, Jiří Hostaš, Said Jalife and Dennis R. Salahub

      Version of Record online: 17 JAN 2018 | DOI: 10.1002/qua.25558

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      Computational chemists seeking to model chemical reactions in complex enzymatic environments are confronted with a myriad of methodological choices. This tutorial review aims to help them find a good computational approach.