Ab initio atom-atom potentials using CamCASP: Theory and application to multipole models for the pyridine dimer

TL;DR

This paper presents a first-principles approach using the CamCASP software to generate accurate atom-atom potentials with explicit polarization for small organic molecules, demonstrated on pyridine dimer.

Contribution

It introduces a novel method for deriving short-range anisotropy parameters using the iterated stockholder atom approach within the CamCASP framework.

Findings

Developed distributed multipole models for pyridine dimer

Derived long-range terms from monomer properties

Established a robust method for short-range anisotropy parameters

Abstract

Creating accurate, analytic atom--atom potentials for small organic molecules from first principles can be a time-consuming and computationally intensive task, particularly if we also require them to include explicit polarization terms, which are essential in many systems. In this first part of a two-part investigation, we describe how the {\sc CamCASP} suite of programs can be used to generate such potentials using some of the most accurate electronic structure methods currently applicable. In particular, we derive the long-range terms from monomer properties, and determine the short-range anisotropy parameters by a novel and robust method based on the iterated stockholder atom approach. We use the techniques described here to develop distributed multipole models for the electrostatic, polarization and dispersion interactions in the pyridine dimer. In the second part of this work we will apply these methods to develop a series of many-body potentials for the pyridine system.