Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

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The powerful independent gradient model (IGM) method has been increasingly popular in visual analysis of intramolecular and intermolecular interactions in recent years. However, we frequently observed that there is an evident shortcoming of IGM map in graphically studying weak interactions, that is its isosurfaces are usually too bulgy; in these cases, not only the graphical effect is poor, but also the color on some areas on the isosurfaces is inappropriate and may lead to erroneous analysis conclusions. In addition, the IGM method was originally proposed based on promolecular density, which is quite crude and does not take actual electronic structure into account. In this article, we propose an improvement version of IGM, namely IGM based on Hirshfeld partition of molecular density (IGMH), which replaces the free-state atomic densities involved in the IGM method with the atomic densities derived by Hirshfeld partition of actual molecular electron density. This change makes IGM have more rigorous physical background. A large number of application examples in this article, including molecular and periodic systems, weak and chemical bond interactions, fullydemonstrate the important value of IGMH in intuitively understanding interactions in chemical systems. Comparisons also showed that the IGMH usually has markedly better graphical effect than IGM and overcomes known problems in IGM. Currently IGMH analysis has been supported in our wavefunction analysis code Multiwfn (http://sobereva.com/multiwfn). We hope that IGMH will become a new useful method among chemists for exploring interactions in wide variety of chemical systems.

This work studies the underlying nature of H‐bonds (HBs) of different types and strengths and tries to predict binding energies (BEs) based on the properties derived from wave function analysis. A total of 42 HB complexes constructed from 28 neutral and 14 charged monomers were considered. This set was designed to sample a wide range of HB strengths to obtain a complete view about HBs. BEs were derived with the accurate coupled cluster singles and doubles with perturbative triples correction (CCSD(T))(T) method and the physical components of the BE were investigated by symmetry‐adapted perturbation theory (SAPT). Quantum theory of atoms‐in‐molecules (QTAIM) descriptors and other HB indices were calculated based on high‐quality density functional theory wave functions. We propose a new and rigorous classification of H‐bonds (HBs) based on the SAPT decomposition. Neutral complexes are either classified as “very weak” HBs with a BE ≥ −2.5 kcal/mol that are mainly dominated by both dispersion and electrostatic interactions or as “weak‐to‐medium” HBs with a BE varying between −2.5 and −14.0 kcal/mol that are only dominated by electrostatic interactions. On the other hand, charged complexes are divided into “medium” HBs with a BE in the range of −11.0 to −15.0 kcal/mol, which are mainly dominated by electrostatic interactions, or into “strong” HBs whose BE is more negative than −15.0 kcal/mol, which are mainly dominated by electrostatic together with induction interactions. Among various explored correlations between BEs and wave function‐based HB descriptors, a fairly satisfactory correlation was found for the electron density at the bond critical point (BCP; ρBCP) of HBs. The fitted equation for neutral complexes is BE/kcal/mol =  − 223.08 × ρBCP/a. u. + 0.7423 with a mean absolute percentage error (MAPE) of 14.7%, while that for charged complexes is BE/kcal/mol =  − 332.34 × ρBCP/a. u. − 1.0661 with a MAPE of 10.0%. In practice, these equations may be used for a quick estimation of HB BEs, for example, for intramolecular HBs or large HB networks in biomolecules. © 2019 Wiley Periodicals, Inc.

Graphically revealing interaction regions in a chemical system enables chemists to quickly recognize where significant interactions have formed. Reduced density gradient (RDG) has already been widely employed in literatures to visually exhibit weak interaction regions, in fact it also has the ability of revealing chemical bonding regions. Unfortunately, RDG cannot clearly show both types of the interactions at the same time. In this work, we propose a new real space function named interaction region indicator (IRI), which is a slight modification on RDG. We found IRI can reveal chemical bonding and weak interaction regions equally well, which brings great convenience in the study of various chemical systems as well as chemical reactions. IRI is also compared with atom-in-molecules (AIM) topology analysis of electron density, it is demonstrated that IRI has the ability to reveal additional interactions to provide chemists a more complete picture. In addition, we put forward a variant of IRI named IRI-π, which is dedicated to reveal interactions of π electrons. It is found that IRI-π can not only distinguish type of π interactions but also exhibit πinteraction strength. IRI and IRI-π have been efficiently implemented in our freely available Multiwfn wavefunction analysis code (http://sobereva.com/multiwfn), and are expected to become new useful members of computational chemists' toolbox in studying chemical problems.

The evaluation of molecular electrostatic potential (ESP) is a performance bottleneck for many computational chemical tasks like RESP charge fitting or QM/MM simulations. In this paper, an efficient algorithm for...

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