Local Temperature as a Chemical Reactivity Descriptor
- 10 June 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry Letters
- Vol. 12 (23), 5623-5630
- https://doi.org/10.1021/acs.jpclett.1c01207
Abstract
Using the electron density and its associated quantities in a molecular system to quantify chemical reactivity in density functional theory is of considerable recent interest. Local temperature based on the kinetic energy density is an intrinsic property of a molecular system, which can be employed for this purpose. In this work, we explore such a possibility. To this end, we examine the local behavior of local temperature with a few choices of the kinetic energy density, apply it to determine regioselectivity of nucleophilic and electrophilic compounds, and then investigate its performance in appreciating reactions along the intrinsic reaction pathway for exothermic, endothermic, and thermoneutral transformations. Our results confirm that local temperature can be used as an effective descriptor of molecular reactivity.Funding Information
- National Natural Science Foundation of China (21503076)
- DST, New Delhi, India (SR/S2/JCB-09/2009)
- Hunan Provincial Natural Science Foundation of China (2017JJ3201)
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