鸟嘌呤前体光谱电化学的计算研究

IF 1.4 Q3 CHEMISTRY, MULTIDISCIPLINARY
Fatemeh Tabesh, H. Sabzyan
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引用次数: 0

摘要

基于鸟嘌呤及其自由基阳离子在模型电极存在下的UV-Vis吸收、荧光、IR和拉曼光谱,使用(TD)M06/6-31++G**方法计算了鸟嘌呤的前体光谱电化学行为。研究了电极电势()、分子-电极距离(d)和分子取向(θ)对这种行为的影响。结果表明,电势的施加会导致分子结构、电荷和自旋密度的分布发生变化,从而改变系统的电子和振动特性。此外,由于施加的电势引起的扰动会改变所研究物种振动带的强度和频率。鸟嘌呤及其自由基阳离子的吸收波长、电子光谱的峰值强度和宽度也显示出对所施加的电极电势的敏感性。溶剂作为静电介质和显式溶剂(分子)的存在对鸟嘌呤的光谱电化学性质有显著影响,并改变电极反应形成的鸟嘌呤自由基阳离子的化学活性。此外,布居和轨道分析表明,对于所有取向,电极施加电势会增加分子间(鸟嘌呤→水)电荷密度位移到UV-Vis转变。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Computational Study of the Precursor Spectroelectrochemistry of Guanine
Precursor spectroelectrochemical behavior of guanine is investigated based on UV-Vis absorption and fluorescence, and IR and Raman spectra of guanine and its radical cation in the presence of a model electrode, computed using (TD)M06/6-31++G** method. Effects of electrode potential ( ), molecule-electrode distance (d) and molecular orientations (θ) on this behavior are investigated. Results indicate that application of electric potential causes changes in the molecular structure and distribution of charge and spin densities, which consequently changes the electronic and vibrational characteristics of the system. Also, perturbation due to the applied electric potential, changes both the intensities and frequencies of the vibrational bands of the studied species. The absorption wavelength, and the peak intensity and width of the electronic spectra of guanine and its radical cation also show sensitivity to the applied electrode potential. Presence of solvent both as electrostatic medium and as explicit solvent (molecules) have significant effects on the spectroelectrochemical properties of guanine, and change the chemical activity of guanine radical cation formed by the electrode reaction. Furthermore, population and orbital analyses show that for all orientations, application of the electric potential by the electrode increases contribution of the inter-molecular (guanine→water) charge density displacement to the UV-Vis transitions.
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来源期刊
Physical Chemistry Research
Physical Chemistry Research CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
2.70
自引率
8.30%
发文量
18
期刊介绍: The motivation for this new journal is the tremendous increasing of useful articles in the field of Physical Chemistry and the related subjects in recent years, and the need of communication between Physical Chemists, Physicists and Biophysicists. We attempt to establish this fruitful communication and quick publication. High quality original papers in English dealing with experimental, theoretical and applied research related to physics and chemistry are welcomed. This journal accepts your report for publication as a regular article, review, and Letter. Review articles discussing specific areas of physical chemistry of current chemical or physical importance are also published. Subjects of Interest: Thermodynamics, Statistical Mechanics, Statistical Thermodynamics, Molecular Spectroscopy, Quantum Chemistry, Computational Chemistry, Physical Chemistry of Life Sciences, Surface Chemistry, Catalysis, Physical Chemistry of Electrochemistry, Kinetics, Nanochemistry and Nanophysics, Liquid Crystals, Ionic Liquid, Photochemistry, Experimental article of Physical chemistry. Mathematical Chemistry.
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