Solution to the pi-Distortivity Problem

Perumalla, Sravanakumar D and Sebastian, Kizhakeyil L (2016) Solution to the pi-Distortivity Problem. In: JOURNAL OF PHYSICAL CHEMISTRY A, 120 (34). pp. 6851-6854.

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Abstract

Traditionally,,the delocalized pi system of benzene is believed to be responsible for its perfectly symmetric D-6h geometry. However, it has also been suggested :that the pi system prefers a distorted D-3h geometry. Arguments for this have been based on clever use of VB methods as well as through shifts in the frequency of the distortive b(2u) mode. Evidence has been provided through different ways of partitioning the total electronic energy between the sigma and the pi systems. These Methods are plagued by the fact that there is no, unique way to partition the energy; leading to questions regarding the validity of the conclusions. Here we note that even though energy cannot be partitioned exactly, force acting on a nucleus depends only on the Single particle density and can hence be partitioned exactly. Using good-quality wave functions that are numerically found to obey the Hellmann-Feynman theorem to good accuracy, we calculate the sigma and pi components of the force and provide conclusive evidence of pi-distortivity at the HE level. Our approach provides an, unambiguous way,to approach the problem with wave functions that account for electron correlation. Our calculations suggest that the conclusion is, valid at the MP2 level, too.

Item Type:	Journal Article
Publication:	JOURNAL OF PHYSICAL CHEMISTRY A
Additional Information:	Copy right for this article belongs to the AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	22 Oct 2016 09:19
Last Modified:	22 Oct 2016 09:19
URI:	http://eprints.iisc.ac.in/id/eprint/55010

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