一類(lèi)染料分子和抗生素分子激發(fā)態(tài)性質(zhì)的理論研究
發(fā)布時(shí)間：2018-08-09 20:21
【摘要】：分子光化學(xué)的研究領(lǐng)域包括分子的光化學(xué)反應(yīng)和分子的光物理變化�；鶓B(tài)分子吸收光子,發(fā)生電子軌道躍遷形成激發(fā)態(tài)。同時(shí)引起分子的幾何構(gòu)型、分子軌道電荷分布、分子極性和偶極矩等激發(fā)態(tài)性質(zhì)發(fā)生改變。因此,研究分子的電子激發(fā)態(tài)的分子結(jié)構(gòu)、電子性質(zhì)和動(dòng)力學(xué)過(guò)程,對(duì)理解染料分子和抗生素分子的光化學(xué)反應(yīng)和光物理過(guò)程,非常重要。抗生素的過(guò)度使用及排放,嚴(yán)重污染水環(huán)境及人類(lèi)健康,通過(guò)激發(fā)態(tài)發(fā)生光化學(xué)反應(yīng)是有效降解方式。本文采用密度泛函和含時(shí)密度泛函理論方法,計(jì)算分子幾何平衡結(jié)構(gòu)、光譜數(shù)據(jù)和前線分子軌道等數(shù)據(jù),比較不同電子態(tài)下的氫鍵強(qiáng)度、幾何構(gòu)型、電子布局?jǐn)?shù)等變化,研究染料分子和抗生素分子的激發(fā)態(tài)結(jié)構(gòu)及性質(zhì)。首先,采用CAM-B3LYP雜化泛函,6-311++G (d,p)基組,CPCM溶劑化模型,研究了對(duì)硝基聯(lián)苯酚-三甲基叔丁基胺氫鍵復(fù)合物的激發(fā)態(tài)性質(zhì)。計(jì)算得到紫外光譜最大吸收峰為333 nm,實(shí)驗(yàn)值為354 nm,符合良好；對(duì)比不同電子態(tài)中氫鍵鍵長(zhǎng)、氫鍵結(jié)合能以及紅外光譜,得到了激發(fā)態(tài)結(jié)構(gòu),發(fā)現(xiàn)了N-H+的生成,驗(yàn)證了實(shí)驗(yàn)中觀測(cè)到的電子-質(zhì)子轉(zhuǎn)移現(xiàn)象；比較電子激發(fā)能和振子強(qiáng)度,說(shuō)明S1態(tài)是主要激發(fā)態(tài)；分析前線分子軌道,說(shuō)明S1態(tài)是分子內(nèi)電荷轉(zhuǎn)移激發(fā)態(tài),具有π-π*躍遷特征,為實(shí)驗(yàn)提供了有用的理論信息。其次,采用B3LYP雜化泛函,6-311-1+G (d,p)基組,水的CPCM溶劑化模型,研究了氯四環(huán)素-水分子氫鍵復(fù)合物的激發(fā)態(tài)性質(zhì)。計(jì)算得到紫外光譜最大吸收峰為370nm,實(shí)驗(yàn)值為367 nm,符合良好；對(duì)比不同電子態(tài)的構(gòu)型和振動(dòng)光譜,發(fā)現(xiàn)在激發(fā)態(tài),分子內(nèi)的電荷轉(zhuǎn)移伴隨著分子間質(zhì)子轉(zhuǎn)移現(xiàn)象,說(shuō)明氯四環(huán)素-水分子相互作用在激發(fā)態(tài)得到增強(qiáng)；比較電子激發(fā)能和振子強(qiáng)度,說(shuō)明主要激發(fā)態(tài)是S2態(tài),且S1態(tài)和S2態(tài)均為是局域激發(fā)態(tài)；分析前線分子軌道,說(shuō)明S1態(tài)和S2態(tài)均為分子內(nèi)電荷轉(zhuǎn)移激發(fā)態(tài)。最后,采用B3LYP雜化泛函,6-311++G(d,p)基組,水的CPCM溶劑化模型的方法,研究了諾氟沙星-水分子氫鍵復(fù)合物的激發(fā)態(tài)性質(zhì)。計(jì)算得到紫外光譜最大吸收峰為277 nm,實(shí)驗(yàn)值為272 nm,計(jì)算紅外光譜C37=038吸收峰1734 cm-1,實(shí)驗(yàn)值1731cm-1,符合良好；對(duì)比不同電子態(tài)中氫鍵鍵長(zhǎng)以及紅外光譜,說(shuō)明分子內(nèi)氫鍵在激發(fā)態(tài)得到增強(qiáng)并且S4態(tài)的分子內(nèi)氫鍵比在S1態(tài)的分子內(nèi)氫鍵更強(qiáng)；比較電子激發(fā)能和振子強(qiáng)度,說(shuō)明主要激發(fā)態(tài)有S1、S2、S4和S6態(tài)；分析前線分子軌道和NBO,說(shuō)明S1態(tài)和S4態(tài)均有π-π*躍遷特征,且S1態(tài)是扭轉(zhuǎn)的分子內(nèi)電荷轉(zhuǎn)移激發(fā)態(tài)。
[Abstract]:The research fields of molecular photochemistry include the photochemical reaction of molecules and the photophysical changes of molecules. The ground state molecule absorbs photons, and the electron orbital transition takes place to form an excited state. At the same time, the molecular geometry, molecular orbital charge distribution, molecular polarity, dipole moment and other excited state properties are changed. Therefore, it is very important to study the molecular structure, electronic properties and kinetic processes of electron-excited states in order to understand the photochemical reactions and photophysical processes of dye molecules and antibiotic molecules. Excessive use and discharge of antibiotics, serious pollution of water environment and human health, photochemical reaction through excited state is an effective way of degradation. In this paper, the density functional and time-dependent density functional theory are used to calculate the molecular geometric equilibrium structure, spectral data and frontier molecular orbital data, and to compare the changes of hydrogen bond strength, geometric configuration and electron distribution number in different electronic states. The excited state structure and properties of dye and antibiotic molecules were studied. Firstly, the excited state properties of p-nitrobiphenol-trimethyl Ding Ji amine hydrogen bond complexes were studied by using the CAM-B3LYP hybrid functional group 6-311G (dapp) solvation model. The maximum absorption peak of UV spectrum is 333 nm and the experimental value is 354 nm, which is in good agreement. Compared with the hydrogen bond length, hydrogen bond binding energy and infrared spectrum of different electronic states, the excited state structure is obtained and the formation of N-H is found. The phenomenon of electron-proton transfer observed in the experiment is verified, the electron excitation energy and oscillator intensity are compared, the S1 state is the main excited state, and the frontier molecular orbital is analyzed, which shows that S1 state is an intramolecular charge transfer excited state with 蟺-蟺 * transition characteristic. It provides useful theoretical information for experiments. Secondly, the excited state properties of chlortetracycline-water molecular hydrogen bond complexes were studied by using the B3LYP hybrid functional group 6-311-1 G (dapp) and the CPCM solvation model of water. The maximum absorption peak of UV spectrum is 370 nm and the experimental value is 367 nm, which is in good agreement. By comparing the configuration and vibrational spectra of different electronic states, it is found that in excited states, intramolecular charge transfer is accompanied by intermolecular proton transfer. The results show that the interaction between chlortetracycline and water is enhanced in the excited state, the electron excitation energy and the oscillator intensity are compared, the main excited state is S2 state, and the S1 state and S2 state are both localized excited states, and the frontier molecular orbitals are analyzed. It shows that both S1 and S2 states are intramolecular charge transfer excited states. Finally, the excited state properties of norfloxacin-water molecular hydrogen bond complexes were studied by using the B3LYP hybrid functional group 6-311G (dapp) and the CPCM solvation model of water. The maximum absorption peak of UV spectrum is 277nm and the experimental value is 272nm.The calculated absorption peak of C37N038 is 1734 cm-1 and the experimental value of 1731cm-1 is in good agreement, and the hydrogen bond length and infrared spectra in different electronic states are compared. The results show that the intramolecular hydrogen bond is strengthened in the excited state and the intramolecular hydrogen bond in S _ 4 is stronger than that in S _ 1.Compared with the electron excitation energy and oscillator strength, the main excited states are S _ (1) S _ (2) S _ (2) S _ (4) and S _ (6). By analyzing frontier molecular orbitals and NBOs, it is shown that both S1 and S4 states have 蟺-蟺 * transition characteristics, and S1 states are torsional intramolecular charge transfer excited states.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O644.11
本文編號(hào)：2175209
[Abstract]:The research fields of molecular photochemistry include the photochemical reaction of molecules and the photophysical changes of molecules. The ground state molecule absorbs photons, and the electron orbital transition takes place to form an excited state. At the same time, the molecular geometry, molecular orbital charge distribution, molecular polarity, dipole moment and other excited state properties are changed. Therefore, it is very important to study the molecular structure, electronic properties and kinetic processes of electron-excited states in order to understand the photochemical reactions and photophysical processes of dye molecules and antibiotic molecules. Excessive use and discharge of antibiotics, serious pollution of water environment and human health, photochemical reaction through excited state is an effective way of degradation. In this paper, the density functional and time-dependent density functional theory are used to calculate the molecular geometric equilibrium structure, spectral data and frontier molecular orbital data, and to compare the changes of hydrogen bond strength, geometric configuration and electron distribution number in different electronic states. The excited state structure and properties of dye and antibiotic molecules were studied. Firstly, the excited state properties of p-nitrobiphenol-trimethyl Ding Ji amine hydrogen bond complexes were studied by using the CAM-B3LYP hybrid functional group 6-311G (dapp) solvation model. The maximum absorption peak of UV spectrum is 333 nm and the experimental value is 354 nm, which is in good agreement. Compared with the hydrogen bond length, hydrogen bond binding energy and infrared spectrum of different electronic states, the excited state structure is obtained and the formation of N-H is found. The phenomenon of electron-proton transfer observed in the experiment is verified, the electron excitation energy and oscillator intensity are compared, the S1 state is the main excited state, and the frontier molecular orbital is analyzed, which shows that S1 state is an intramolecular charge transfer excited state with 蟺-蟺 * transition characteristic. It provides useful theoretical information for experiments. Secondly, the excited state properties of chlortetracycline-water molecular hydrogen bond complexes were studied by using the B3LYP hybrid functional group 6-311-1 G (dapp) and the CPCM solvation model of water. The maximum absorption peak of UV spectrum is 370 nm and the experimental value is 367 nm, which is in good agreement. By comparing the configuration and vibrational spectra of different electronic states, it is found that in excited states, intramolecular charge transfer is accompanied by intermolecular proton transfer. The results show that the interaction between chlortetracycline and water is enhanced in the excited state, the electron excitation energy and the oscillator intensity are compared, the main excited state is S2 state, and the S1 state and S2 state are both localized excited states, and the frontier molecular orbitals are analyzed. It shows that both S1 and S2 states are intramolecular charge transfer excited states. Finally, the excited state properties of norfloxacin-water molecular hydrogen bond complexes were studied by using the B3LYP hybrid functional group 6-311G (dapp) and the CPCM solvation model of water. The maximum absorption peak of UV spectrum is 277nm and the experimental value is 272nm.The calculated absorption peak of C37N038 is 1734 cm-1 and the experimental value of 1731cm-1 is in good agreement, and the hydrogen bond length and infrared spectra in different electronic states are compared. The results show that the intramolecular hydrogen bond is strengthened in the excited state and the intramolecular hydrogen bond in S _ 4 is stronger than that in S _ 1.Compared with the electron excitation energy and oscillator strength, the main excited states are S _ (1) S _ (2) S _ (2) S _ (4) and S _ (6). By analyzing frontier molecular orbitals and NBOs, it is shown that both S1 and S4 states have 蟺-蟺 * transition characteristics, and S1 states are torsional intramolecular charge transfer excited states.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O644.11
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相關(guān)期刊論文 前6條
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