Ab-initio Study Aiming Some Spectroscopic and Electronic Properties of 2-[(1H-benzimidazol-1-yl)- methyl]benzoic acid

Year 2022, Volume: 4 Issue: 2, 209 - 223, 31.12.2022

Eylem Çelik , Pinar Tasli , Sevgi Özdemir Kart

Abstract

In this study, our main aim to characterize the title molecule of C15H12N2O2 by using quantum chemistry computational method. We have performed ab-initio simulations to determine the quantized energy levels of molecules, ions or nuclei, which enable to obtain its structural parameters and, some spectroscopic, electronic and thermal properties. The compound is optimized by using ab-initio method based on the density functional theory (DFT)/B3LYP with 6-31G(d,p) basis set implemented in Gaussian 09W subprogram. The geometric parameters of bond length, bond angle and dihedral angle computed are in good agreement with those of available experiment. The same basis set and computational method have been utilized for the vibrational spectra of the title compound by using the optimized structure. The marking of the vibrational frequencies of the molecule have been carried out via the VEDA4 program (Vibrational Energy Distribution Analysis). The title molecule has 31 atoms and 87 fundamental vibrational modes, with the most bending vibrations. Since experimental chemical shifts are generally obtained in DMSO (Dimethyl Sulfoxide) and Acetonitrile solutions, the 1H and 13C NMR chemical shifts of the molecule in the same solutions are computed by using the Gauge-Independent Atomic Orbital (GIAO) approach applying DFT/B3LYP method with the basis set of 6-31G (d,p). Moreover, UV-Vis spectral analysis of the studied molecule have been investigated in both of the DMSO and Acetonitrile solvents. The maximum absorption peaks of compound have been evaluated by the Time Dependent Self-Consistent Field (TD-SCF)/DFT/B3LYP/6-31G(d,p) method. A single absorbance without any shoulder at 257 nm in both solvent have been observed. At last, electronic properties such as chemical hardness/softness, ionization potential, highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy levels, electronegativity and energy bandgap have been predicted. Our results from DFT calculations not only aid in the interpretation of available experimental data, but also illuminate the spectroscopic and electronic properties of the title molecule in detail.

Keywords

Benzoic acid, DFT, vibrational spectroscopy, UV-Vis and NMR spectral analyzes, UV-Vis and NMR spectral analyzes,

Supporting Institution

Pamukkale University

Project Number

2018FEBE052

2-[(1H-benzimidazol-1-il)-metil]benzoik asit Molekülüne Ait Bazı Spektroskopik ve Elektronik Özellikleri Üzerine Ab-initio Çalışması

Abstract

u çalışmada temel amacımız, kuantum kimyası hesaplama yöntemini kullanarak C15H12N2O2 başlık molekülünü karakterize etmektir. Moleküllerin, iyonların veya çekirdeklerin, yapısal parametrelerinin ve bazı spektroskopik, elektronik ve termal özelliklerinin elde edilmesini sağlayan nicelleştirilmiş enerji seviyelerini belirlemek için ab-initio simülasyonları gerçekleştirdik. Bileşik, Gaussian 09W alt programında uygulanan 6-31G(d,p) temel seti ile yoğunluk fonksiyonel teorisi (DFT)/B3LYP'ye dayalı ab-initio yöntemi kullanılarak optimize edilmiştir. Hesaplanan bağ uzunluğu, bağ açısı ve dihedral açının geometrik parametreleri, mevcut deneyinkilerle iyi bir uyum içindedir. Optimize edilmiş yapı kullanılarak başlık bileşiğinin titreşim spektrumları için aynı temel set ve hesaplama yöntemi kullanılmıştır. Molekülün titreşim frekanslarının işaretlenmesi VEDA4 programı (Vibrational Energy Distribution Analysis) ile yapılmıştır. Başlık molekülü 31 atoma ve en çok bükülme titreşimine sahip 87 temel titreşim moduna sahiptir. Deneysel kimyasal kaymalar genellikle DMSO (Dimetil Sülfoksit) ve Asetonitril çözeltilerinde elde edildiğinden, molekülün aynı çözeltilerdeki 1H ve 13C NMR kimyasal kaymaları DFT/B3LYP yöntemi uygulanarak Gauge-Bağımsız Atomik Yörünge (GIAO) yaklaşımı kullanılarak hesaplanmıştır. 6-31G (d,p) temel seti ile. Ayrıca, çalışılan molekülün UV-Vis spektral analizi hem DMSO hem de Asetonitril çözücülerde araştırılmıştır. Bileşiğin maksimum absorpsiyon zirveleri, Zamana Bağlı Kendinden Tutarlı Alan (TD-SCF)/DFT/B3LYP/6-31G(d,p) yöntemi ile değerlendirilmiştir. Her iki çözücüde de 257 nm'de herhangi bir omuz olmaksızın tek bir absorbans gözlenmiştir. Son olarak, kimyasal sertlik/yumuşaklık, iyonlaşma potansiyeli, en yüksek dolu moleküler orbital (HOMO)-en düşük boş moleküler orbital (LUMO) enerji seviyeleri, elektronegatiflik ve enerji bant aralığı gibi elektronik özellikler tahmin edilmiştir. DFT hesaplamalarından elde ettiğimiz sonuçlar, yalnızca mevcut deneysel verilerin yorumlanmasına yardımcı olmakla kalmaz, aynı zamanda başlık molekülünün spektroskopik ve elektronik özelliklerini ayrıntılı olarak aydınlatır.

Keywords

Benzoik asit, titreşim spektroskopisi, UV-Vis ve NMR spektral analizleri, DFT

Project Number

2018FEBE052

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