Investigation of Dependence of Electronic Structure, Spectroscopic Features, and Interionic Weak Interactions on Alkyl Chain Length in [CnC1im][NTF2] (n=1,2, .. 8) Ionic Liquids

Year 2017, Volume: 17 Issue: 3, 1181 - 1191, 29.12.2017

Fehmi Bardak

Abstract

In this work, electronic structure and some physical and optical properties [CnC1im][NTf2][1-alkyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide] (n = 1, 2, ... 8) were investigated theoretically via density functional theory calculations within the dependency of alkyl chain length. Geometrical structure and frequency calculations along with population analysis were performed at DFT-B3LYP/6- 311G(d,p) level of theory. Inter- and intra-molecular hydrogen bonding and van der Waals interactions were visualized by using reduced density gradient analysis. Geometrical structure and vibrational features were analyzed in detail for the strong interaction regions, and their relation to nano structural organization was explored. Characteristics of interionic interactions were fingerprinted on the basis of Becke surface and Hirshfeld analysis. Electronic transition properties were investigated by time dependent density functional theory. The reason for colored appearance comes with elongation of chain length is explained through absorbance spectra.

Keywords

Ionic liquid, DFT, TDDFT, Weak Interaction analysis, Nano structural organization

[CnC1im][NTF2] (n = 1, 2, … 8) İyonik Sıvılarında Elektronik Yapı, Spektroskopik Özellikler ve İyonlar Arası Zayıf Etkileşmelerin Alkali Zincir Uzunluğuna Bağlılığının İncelenmesi

Abstract

Bu çalışmada, [CnC1im][NTf2][1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] (n = 1, 2, … 8) için değişen alkali zincir uzunluğuna göre elektronik yapı, bazı fiziksel ve optik özelliklerin değişimi yoğunluk fonksiyonu teorisi (DFT) metotları kullanarak teorik olarak incelendi. Geometrik yapı ve frekans hesaplamaları popülasyon analizi ile birlikte DFT-B3LYP/6-311G(d,p) teori ve baz seti kullanılarak yapıldı. İndirgenmiş yoğunluk değişimleri analizi yapılarak iyon içi ve iyonlar arası hidrojen bağlanmaları ve van der Waals etkileşmeleri görüntülendi. Etkileşmelerin yoğun olduğu bölgeler için geometrik yapı ve titreşimsel özellikleri analiz edilerek nano yapısal organizasyonla ilişkisi araştırıldı. Becke yüzeyi ve Hirsfeld analizi temel alınarak iyonlar arası etkileşmelerin karakteristikleri tanımlandı. Elektronik geçiş özellikleri zamana bağlı yoğunluk fonksiyonu teorisi kullanılarak incelendi. Soğurma spektrumları ile iyonik sıvılarda zincir uzunluğuna bağlı olarak gözlenen renk değişimlerinin sebebi açıklandı.

Keywords

İyonik sıvı, DFT, TD-DFT, Zayıf etkileşme analizi, Nano yapısal organizasyon

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