Theoretical examination of the conformational effect on the molecular structure and electronic properties of the orthorhombic metaboric acid molecule

Abstract

In the present study, conformational analysis, Nonlinear Optical (NLO) behavior, vibrational spectra, electronic and the molecular structure of orthorhombic metaboric acid have been investigated comprehensively by using ab initio Hartree Fock (HF) and Density Functional Theory DFT at the B3LYP level with 6-311++G(d, p) basis set. The conformational analysis was performed in detail for the first time as a function of both the φ (B1-O1-H) bond angle and the ψ (O6-B1-O1-H) dihedral angle. The results of calculated potential energy curves show that the molecule has two conformers (C-I and C-II Conformer) with minimum energies in a stable form. C-I conformer is a more stable form than C-II conformer. Linear and nonlinear optical properties of conformer C-I and C-II of the orthorhombic metaboric acid molecule are examined by the determination of the electric dipole moment μ, the polarizability α, and the hyperpolarizability β both methods. The optimized molecular structures of C-I and C-II conformer of the molecule belong to C3h and Cs symmetry, respectively. The dipole moment values for conformer C-II with Cs symmetry obtained using B3LYP/6-311++G(d, p) and HF/6-311++G(d, p) methods were found to be 2.95 and 3.07 Debye, Whereas, for C-I conformer with C3h symmetry, the values obtained using the same methods are found equal (0.0 Debye). Total energy distributions (TED) were calculated to find assignments of calculated vibration modes of both conformers by using VEDA 4f program. It was observed that there is a good agreement between the experimental data in the literature and the calculated structural parameters.  

Keywords

• B3LYP,
• C3h
• Conformational analysis
• NLO
• Orthorhombic metaboric acid

Ortorombik metaborik asit molekülünün moleküler yapısı ve elektronik özellikleri üzerindeki konformasyonel etkinin teorik olarak incelenmesi

Abstract

Bu çalışmada, ortorombik metaborik asit molekülünün konformasyon analizi, doğrusal olmayan optik davranışı, titreşim spektrumları, elektronik ve moleküler yapısı ab initio Hartree Fock (HF) ve Yoğunluk Fonksiyonel Teorisi DFT/B3LYP temel seviyesinde (6-311++G(d,p) temel seti kullanılarak kapsamlı bir şekilde araştırıldı. Konformasyon analizi hem φ (B1-O1-H) bağ açısı, hem de ψ (O4-B1-O1-H) dihedral açısının fonksiyonu olarak ilk kez detaylı olarak yapıldı. Hesaplanan potansiyel enerji eğrilerinin sonuçları, molekülün minimum enerjili iki kararlı konformere (C-I ve C-II konformer) sahip olduğunu gösterdi. C-I konformeri C-II konformerinden daha kararlıdır. Ortorombik metaborik asit molekülünün C-I ve C-II konformerlerinin doğrusal ve doğrusal olmayan optik özellikleri, elektrik dipol momenti μ, polarizebilite α ve hiperpolarizebilitesi β her iki yöntem ile incelenmiştir. Molekülün C-I ve C-II konformerlerinin optimize edilmiş moleküler yapıları, sırasıyla, C3h ve Cs simetrisine sahiptir. Cs simetrisine sahip C-II konformeri için B3LYP/6-311++G(d,p) ve HF/6-311++G(d,p) yöntemleri kullanılarak elde edilen dipol momenti değerleri 2,95 ve 3,07 Debyedir. Oysa C3h simetrisine sahip C-I konformeri için aynı yöntemler kullanılarak elde edilen değerlerin eşit olduğu (0,0 Debye) bulunmuştur. Her iki konformerin titreşim modlarının işaretlenmesini bulmak için toplam enerji dağılımı (TED) VEDA 4f programı kullanılarak hesaplanmıştır. Literatürdeki deneysel veriler ile hesaplanan yapısal parametreler arasında iyi bir uyum olduğu görülmüştür.

Keywords

• B3LYP
• C3h
• Konformasyon analizi
• NLO
• Ortorombik metaborik asit

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