Linear response function of the Mayer bond order: an indicator to describe intrinsic chemical reactivity of molecules

Abstract

We here formulate and implement linear response function (LRF) of the Mayer bond order (MBO), which is expected to be a new indicator to describe intrinsic chemical reactivity of molecules. We calculate LRFs of the MBOs of para-substituted benzoic acids, and compare the results with the Hammett substituent constants and computational results of acid dissociation constants that were previously reported. The results are discussed from the viewpoint of the applicability of LRF of the MBO to estimate the relative reactivity of the substituted benzoic acids.

Keywords:

• Mayer bond order
• linear response function
• Hammett substituent constant
• chemical reactivity
• ab initio calculation

Acknowledgements

We acknowledge an anonymous referee for valuable comments, particularly on the theoretical description of various types of bond orders and for suggesting that we should use basis functions without diffuse functions to improve computational results of the LRF of the MBO.

Additional information

Funding

This work is partly supported by a grant from Japan Science and Technology Agency (JST) with a Core Research for Evolutional Science and Technology (CREST).