{"title":"鸟嘌呤前体光谱电化学的计算研究","authors":"Fatemeh Tabesh, H. Sabzyan","doi":"10.22036/PCR.2020.217921.1727","DOIUrl":null,"url":null,"abstract":"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.","PeriodicalId":20084,"journal":{"name":"Physical Chemistry Research","volume":null,"pages":null},"PeriodicalIF":1.4000,"publicationDate":"2020-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Computational Study of the Precursor Spectroelectrochemistry of Guanine\",\"authors\":\"Fatemeh Tabesh, H. Sabzyan\",\"doi\":\"10.22036/PCR.2020.217921.1727\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"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.\",\"PeriodicalId\":20084,\"journal\":{\"name\":\"Physical Chemistry Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2020-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Research\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.22036/PCR.2020.217921.1727\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Research","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.22036/PCR.2020.217921.1727","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
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.
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.