Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects
TL;DR: In this article, a method is presented which utilizes the calculation of the molecular electrostatic potential or the electric field at a discrete number of preselected points to evaluate the environmental effects of a solvent on the properties of a molecular system.
About: This article is published in Chemical Physics.The article was published on 1981-02-01. It has received 7618 citations till now. The article focuses on the topics: Implicit solvation & Solvent effects.
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TL;DR: This paper presents a meta-modelling procedure called "Continuum Methods within MD and MC Simulations 3072", which automates the very labor-intensive and therefore time-heavy and expensive process of integrating discrete and continuous components into a discrete-time model.
Abstract: 6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072
13,286 citations
TL;DR: The SMD model may be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space, including, for example, the conductor-like screening algorithm.
Abstract: We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute−solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonho...
10,945 citations
TL;DR: In this paper, a new integral equation formulation of the polarizable continuum model (PCM) is presented, which allows one to treat in a single approach dielectrics of different nature: standard isotropic liquids, intrinsically anisotropic medialike liquid crystals and solid matrices, or ionic solutions.
Abstract: We present a new integral equation formulation of the polarizable continuum model (PCM) which allows one to treat in a single approach dielectrics of different nature: standard isotropic liquids, intrinsically anisotropic medialike liquid crystals and solid matrices, or ionic solutions. The present work shows that integral equation methods may be used with success also for the latter cases, which are usually studied with three-dimensional methods, by far less competitive in terms of computational effort. We present the theoretical bases which underlie the method and some numerical tests which show both a complete equivalence with standard PCM versions for isotropic solvents, and a good efficiency for calculations with anisotropic dielectrics.
5,760 citations
TL;DR: In this article, an efficient version of the polarizable continuum solvation model was implemented in the GAUSSIAN94 package, which exploits a new definition of surface elements area, and a direct formulation of the electrostatic self-consistent problem.
2,978 citations
TL;DR: A major revival in the use of classical electrostatics as an approach to the study of charged and polar molecules in aqueous solution has been made possible through the development of fast numerical and computational methods to solve the Poisson-Boltzmann equation for solute molecules that have complex shapes and charge distributions.
Abstract: A major revival in the use of classical electrostatics as an approach to the study of charged and polar molecules in aqueous solution has been made possible through the development of fast numerical and computational methods to solve the Poisson-Boltzmann equation for solute molecules that have complex shapes and charge distributions. Graphical visualization of the calculated electrostatic potentials generated by proteins and nucleic acids has revealed insights into the role of electrostatic interactions in a wide range of biological phenomena. Classical electrostatics has also proved to be successful quantitative tool yielding accurate descriptions of electrical potentials, diffusion limited processes, pH-dependent properties of proteins, ionic strength-dependent phenomena, and the solvation free energies of organic molecules.
2,740 citations
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TL;DR: In this article, an extended basis set of atomic functions expressed as fixed linear combinations of Gaussian functions is presented for hydrogen and the first row atoms carbon to fluorine, where each inner shell is represented by a single basis function taken as a sum of four Gaussians and each valence orbital is split into inner and outer parts described by three and one Gaussian function, respectively.
Abstract: An extended basis set of atomic functions expressed as fixed linear combinations of Gaussian functions is presented for hydrogen and the first‐row atoms carbon to fluorine. In this set, described as 4–31 G, each inner shell is represented by a single basis function taken as a sum of four Gaussians and each valence orbital is split into inner and outer parts described by three and one Gaussian function, respectively. The expansion coefficients and Gaussian exponents are determined by minimizing the total calculated energy of the atomic ground state. This basis set is then used in single‐determinant molecular‐orbital studies of a group of small polyatomic molecules. Optimization of valence‐shell scaling factors shows that considerable rescaling of atomic functions occurs in molecules, the largest effects being observed for hydrogen and carbon. However, the range of optimum scale factors for each atom is small enough to allow the selection of a standard molecular set. The use of this standard basis gives theoretical equilibrium geometries in reasonable agreement with experiment.
8,551 citations
4,775 citations
TL;DR: In this paper, the electrical contribution to the chemical potential of an ion having an arbitrary charge distribution is calculated with the aid of the Debye-Huckel theory, and the calculation is based upon a general solution in polar coordinates of the approximate Debye Huckel equation, Δψ-κ2ψ=0.
Abstract: The electrical contribution to the chemical potential of an ion having an arbitrary charge distribution is calculated with the aid of the Debye‐Huckel theory. The calculation is based upon a general solution in polar coordinates of the approximate Debye‐Huckel equation, Δψ—κ2ψ=0. In addition, the Born relation between the free energy of solvation of a spherical ion and the dielectric constant of the solvent, is generalized to include ions of arbitrary charge distribution. Application of the theory to a study of the influence of simple electrolytes, and of the dielectric constant of the solvent on the solubilities of the aliphatic amino‐acids in alcohol water mixtures, is discussed.
1,375 citations
TL;DR: In this paper, a model that relies on the knowledge of the molecular electrostatic potential, which is derived from a molecular wave function by using the usual methods for calculating the mean expectation value of an operator, is discussed.
Abstract: Publisher Summary This chapter discusses a model that relies on the knowledge of the molecular electrostatic potential, which is derived from a molecular wavefunction by using the usual methods for calculating the mean expectation value of an operator. In its basic premises the model employs quantum mechanics, with only the approximations necessary in molecular quantal calculations. The model is also discussed regarding its relationships with the Hellmann–Feynman theorem. The electrostatic potential V itself is examined in order to show how the electrostatic potential reflects the characteristics of the electronic distribution of a molecule and then the reliability of V is discussed as a reactivity index. The shape of the electrostatic potential and its relationship to the electronic molecular structure is discussed with the aid of various examples. One of them includes the glycine tautomers and the corresponding anion example. The chapter also discusses the electrostatic molecular potential in terms of local group contributions.
1,116 citations
578 citations