Konumsal İzomerizmin Etkilerine İlişkin Teorik Görüşler: DFT/TD-DFT Yaklaşımı

Year 2023, Issue: 52, 122 - 135, 15.12.2023

Sümeyya Serin Öznur Doğan Ulu

Abstract

Fonksiyonel grupların veya sübstitüentlerin aynı karbon iskeletinde farklı konumları işgal etmesiyle konumsal izomerizm olgusu ortaya çıkmaktadır. Moleküler formül aynı kaldığı halde molekül içindeki atomların dizilişi farklıdır. Bu durum fiziksel ve kimyasal özelliklerde farklılıklara yol açar. Bu bağlamda, mevcut çalışma, 3-formilasetilasetonun orto-, meta- ve para-aminobenzoik asitlerle etkileşiminden elde edilen üç izomerin (1-3) özelliklerinin hesaplamalı kimya yöntemleri kullanılarak incelenmesini amaçlamaktadır. Konumsal izomerinin, termodinamik parametreler, fizikokimyasal büyüklükler, reaktivite indisleri, elektrostatik yüzey özellikleri ve molekül içi etkileşimler üzerindeki etkilerini araştırmak için Yoğunluk Fonksiyonel Teorisi (YFT) çalışması yapıldı. Ayrıca, temel ve uyarılmış durum özelliklerini incelemek için TD-DFT yöntemi kullanılmıştır. Her üç izomerin hesaplanan ∆E (toplam enerji), ∆H (entalpi) ve ∆G (Gibbs serbest enerjisi) değerlerinde kaydadeğer değişikler gözlenmemiştir. Buna karşın, sınır moleküler orbital analizi sonucunda kuantum kimyasal reaktivite tanımlayıcılarının farklılık gösterdiği belirlenmiştir.

Keywords

Konumsal İzomerizm, Aminobenzoik Asit, YFT, Reaktivite

Theoretical Insights into the Effects of Positional Isomerism: DFT/TD-DFT Approach

Abstract

The phenomenon of positional isomerism arises when functional groups or substituents occupy different positions in the same carbon skeleton. Although the molecular formula remains the same, the arrangement of atoms in the molecule is different. This leads to differences in physical and chemical properties. In this context, the present study aims to investigate the properties of the three isomers (1-3) obtained from the interaction of 3-formylacetylacetone with ortho-, meta- and para-aminobenzoic acids using computational chemistry methods. Density Functional Theory (DFT) study was carried out to explore the effects of positional isomerism on thermodynamic parameters, physicochemical quantities, reactivity indices, electrostatic surface properties and intramolecular interactions. Also, the TD-DFT method was used in order to examine ground and excited state characteristics. No significant changes were observed in the computed ∆E (total energy), ∆H (enthalpy), and ∆G (Gibbs free energy) values of all three isomers. On the other hand, as a result of the frontier molecular orbital analysis, it was determined that the quantum chemical reactivity descriptors differed.

Keywords

Positional Isomerism, Aminobenzoic Acid, DFT, Reactivity

Thanks

The numerical calculations reported in this paper were fully performed at TUBITAK ULAKBIM, High Performance and Grid Computing Center (TRUBA resources).

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