Spektroscopic, Geometric, Termodynamic and Electronic Analysis with DFT(B3LYP/B3PW91)/HF of 3-Phenyl-5-(4-pyridyl)-1,2,4-triazole Molecule

Abstract

The molecular geometric optimization of 3-Phenyl-5-(4-pyridyl)-1,2,4-triazole compound was obtained using DFT(B3LYP, B3PW91)/ HF methods at the 6-311G(d,p) and 3-21G basis sets. Thus, the most stable geometric conformer of the compound was found by various methods and sets. The experimental spectral investigations were performed using FT-IR values and 1H/13C-NMR chemical shifts. Geometric structure analyses (bond angles, bond lengths), Proton/Carbon NMR chemical shifts, thermodynamic parameters, HOMO-LUMO analyses, electronic properties, mulliken charges, vibrational wavenumbers, dipole moment, total energy of the title molecule were calculated using"Gaussian 09W"software package. The results were improved at the GaussView5.0 program. Computation IR data was determined at the Veda4f program and these harmonic vibrational frequencies were scaled with definite factor. Experimental data obtained from the literature. The experimental spectral values were compared with computed IR data. Proton Nuclear Magnetic Resonance (1H-NMR) and Carbon-13 Nuclear magnetic Resonance (13C-NMR) spectral values was calculated in gas phase and in DMSO solvent according to GIAO method. These values were compared with experimental proton/ carbon NMR data and regression analysis were performed according to the results. Also, the theoretical results obtained with different methods and functional were compared with each other. Furthermore, parameters such as chemical hardness (η), electronegativity (χ), ionization potential (I), chemical softness (σ), electron affinity (A) were determined with HOMO-LUMO energies calculations. The molecular surfaces such as the electron density, the electron spin potential (ESP), molecular electrostatic potential (MEP), the total density and contour maps were designated. Thus, all theoretical parameters of molecule were calculated with different methods, functionals and sets. In the result, these data were compared and the most appropriate method and set were found.

Keywords

• 1,2,4-Triazole
• B3LYP
• B3PW91
• HOMO-LUMO
• GIAO

3-Fenil-5-(4-pridil)-1,2,4-triazol Molekülünün DFT(B3LYP/B3PW91)/HF ile Spektroskopik, Geometrik,Termodinamik ve Elektronik Analizi

Öz

3-Fenil-5-(4-pridil)-1,2,4-triazol bileşiğinin moleküler geometrik optimizasyonu 6-311G(d,p) ve 3-21G temel setinde DFT(B3LYP, B3PW91)/ HF metodları  kullanılarak elde edilmiştir. Böylece, bileşiğin en kararlı geometrik şekli çeşitli metod ve setlerle  bulunmuştur. Deneysel spektral incelenmeler FT-IR değerleri ve ¹H/ ¹³C-NMR kimyasal kaymaları kullanılarak gerçekleştirilmiştir. Geometrik yapı analizleri (bağ açıları, bağ uzunlukları), Proton/ Karbon NMR kimyasal kaymaları, termodinamik parametreler, HOMO-LUMO analizleri, elektronik özellikler, mulliken yükleri, titreşimsel dalgalanmalar, dipol momenti, başlıca molekülünün toplam enerjisi "Gaussian 09W" paket programı  kullanılarak hesaplanmıştır.  Sonuçlar,  GaussView5.0 programında  değerlendirilmiştir.  Hesaplamalı IR verileri Veda4f programında belirlenmiş ve bu hormonik titreşim frekansları belirli faktörler ile ölçeklendirilmiştir. Deneysel değerler literatürden alınmıştır. Deneysel spektral değerler hesaplanan IR verileri ile karşılaştırılmıştır. Proton Nükleer Manyetik Rezonans (¹H-NMR) ve Karbon-13 Nükleer Manyetik Rezonans (¹³C-NMR) spektral değerleri, gaz fazında ve DMSO çözücüsünde GIAO yöntemine göre hesaplanmıştır. Bu değerler deneysel proton / karbon nmr verileriyle karşılaştırılmış ve sonuçlara göre regresyon analizi yapılmıştır. Ayrıca farklı yöntemlerle elde edilen ve fonksiyonel olan teorik sonuçlar birbiriyle karşılaştırılmıştır. Bundan başka, HOMO-LUMO enerji hesaplamaları ile kimyasal sertlik (η), elektronegatiflik (χ), iyonlaşma potansiyeli (I), kimyasal yumuşaklık (σ), elektron ilgisi (A) gibi parametreler belirlenmiştir. Elektron yoğunluğu moleküler yüzeyler, elektron spin potansiyeli (ESP), moleküler elektrostatik potansiyel (MEP), toplam yoğunluk ve kontur haritaları belirlenmiştir. Böylece farklı metodlar, fonksiyonlar ve setler ile molekülün tüm teorik parametreleri hesaplanmıştır. Sonuçta bu veriler karşılaştırılmış ve en uygun yöntem ve set bulunmuştur.

Anahtar Kelimeler

• 1.2.4-Triazol
• B3LYP
• B3PW91
• HOMO-LUMO
• GIAO

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