Theoretical Investigation of The Molecular Structure, Conformational and Nonlinear Optical Properties of Picolinic Acid and Its Derivatives

Abstract

In this paper, ab initio Hartree-Fock (HF) and Density Functional Theory (DFT), using Becke-3–

Lee–Yang–Parr (B3LYP) hybrid density functional, calculations have been performed to characterize the ground

state geometrical energy, the dipole moment (μ), polarizability (α), the hyperpolarizability (β) of picolinic acid

(PA), picolinamide (PAA) and picolinic acid hydrazide (PAH) molecules using the 6-311++G (d, p) basis set.

The 1H and 13C NMR chemical shifts were calculated by GIAO approach by using B3LYP/6-311+G (2d, p) and

HF/6-31G (d) level of theory. Also, EHOMO (the highest occupied molecular orbital energy), ELUMO (the lowest

unoccupied molecular orbital energy), HOMO-LUMO energy gap (ΔEg), the dipole moment (μ), polarizability (α)

and the hyperpolarizability (β) are investigated as a function of the torsional angle, for each molecule. In addition,

the trends in the calculated torsional potentials, barrier heights and energy differences between conformers are

discussed. The trans-conformers of the studied molecules were found to be most stable among their conformers.

The potential barrier height of cis- conformers are at 13.24, 10.69, and 9.56 with DFT/B3LYP level of the theory

6-311++G (d, p) basis set and at the HF/6-311++ G (d, p) 13.53, 10.94, and 10.55 kcal/mol, respectively. The

structural parameters of the studied molecule compared with the data given in the literature.

Keywords

• Picolinic acid,DFT calculation,NMR,Non-linear optical properties

Pikolinik Asit ve Türevlerinin Moleküler Yapısının, Konformasyonel ve Doğrusal Olmayan Optik Özelliklerinin Teorik Olarak İncelenmesi

Abstract

Bu çalışmada, Pikolinik asit (PAA), pikolinamid (PAA) ve pikolinik asit hidrazid (PAH) moleküllerinin taban

(temel) durum geometrik enerjisini, dipol momenti (μ), polarizebilitesi (α) ve hiperpolarizebilitesini (β) belirlemek

için ab-initio Hartree–Fock (HF) ve Becke-3-Lee-Yang-Parr (B3LYP) hibrit fonksiyonelli Yoğunluk Fonksiyoneli

Teorisi (DFT) ile 6-311++G(d,p) temel seti kullanılarak hesaplamalar yapılmıştır. 1H ve 13C NMR kimyasal kayma

hesaplamaları GIAO yaklaşımına göre B3LYP/6-311+G (2d, p) ve HF/6-31G (d) yöntemleri ile yapılmıştır. Ayrıca,

her molekül için, EHOMO (en yüksek dolu moleküler orbital enerjisi) ve ELUMO (en düşük boş moleküler orbital

enerjisi), ELUMO-EHOMO enerji gap (ΔEg), dipol momenti (μ), polarizebilite (α) ve hiperpolarizebilite (β) değerleri

torsiyon açının fonksiyonu olarak araştırıldı. Bunlara ek olarak, Konformerler arasındaki hesaplanmış torsiyonal

potansiyelleri, bariyer yükseklikleri ve enerji farkları tartışıldı. Çalışılan moleküllerin trans-konformerlerinin

konformerler arasında en kararlı oldukları bulundu. Cis-konformers durumunda potansiyel bariyer yüksekliğinin

DFT / B3LYP/6-311 ++ G (d, p) yönteminde 13.24, 10.69 ve 9.56 olduğu, HF / 6-311++G (d, p) yönteminde

ise 13.53, 10.94 ve 10.55 kkal / mol olduğu sırasıyla bulunmuştur. Çalışılan molekülün yapısal parametreleri,

literatürde verilen verilerle karşılaştırılmıştır.

Keywords

• Pikolinik asit,DFT hesaplama,NMR,Nonlineer optik özellikler

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