Related Experiment Video
Updated: Mar 30, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Isotropic Periodic Sum Treatment of Long-Range Electrostatic Interactions in Combined Quantum Mechanical and
1Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis , 402 N. Blackford St., LD326, Indianapolis, Indiana 46202, United States.
Abstract:
The isotropic periodic sum (IPS) method was extended to describe long-range electrostatic interactions in combined quantum mechanical and molecular mechanical (QM/MM) calculations. The resulting method, designated QM/MM-IPS, was tested for two ion association processes and a model SN2 reaction in aqueous solution. Potential of mean force (PMF) profiles and radial distribution functions computed from the QM/MM-IPS simulations were compared with those obtained by using the existing QM/MM-Ewald sum and cutoff (QM/MM-Cutoff) methods. In contrast to the QM/MM-Cutoff method, with which PMFs of ion separation tend to display a spurious linear drift, the QM/MM-IPS method successfully eliminates such artifacts, in excellent agreement with the QM/MM-Ewald results. The PMF obtained with the QM/MM-IPS method for the SN2 reaction that transfers an NH3 group between two chloride anions closely resembles that from the QM/MM-Ewald simulations. Compared with QM/MM-Ewald, the QM/MM-IPS method reduces the computational cost by 60-70% when a local region of 12 to 14 Å is used. These results suggest that the QM/MM-IPS method can be used as a reliable and efficient alternative to the QM/MM-Ewald method to incorporate long-range electrostatic effects in simulating solution-phase chemical reactions.
Related Concept Videos
Molecular Orbital Theory I
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration
According to Hooke's law, the vibrational frequency is directly proportional to...
Electrostatic Boundary Conditions in Dielectrics
Consider a case where both the mediums across a boundary are two different dielectric materials. Recall that the electric field and electric displacement are proportional and related through the material's permittivity....
¹H NMR: Long-Range Coupling
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
Molecular Orbital Theory II
The Debye–Hückel Theory of Electrolyte Solutions

