甲醛与碱金属离子、异烟肼与有机小分子相互作用激发态的理论研究
发布时间：2019-06-17 20:10
【摘要】：分子间相互作用力在许多物理和化学、生物过程中具有十分重要的作用,在过去几十年间引起了科研工作者们的广泛关注。近年来,人们发现激发态的超分子在光物理和光化学过程中有着特殊的性质。本文用密度泛函理论与含时密度泛函理论,对(1)甲醛与碱金属离子的激发态复合物(2)异烟肼与甲醛的激发态复合物(3)异烟肼与甲醇的激发态复合物三个体系进行理论研究。文中利用不同的方法分析了甲醇与碱金属离子、异烟肼与有机小分子之间的弱相互作用力、激发态弱键的成键本质,并系统地分析了分子间弱相互作用力形成后对单体的影响以及电子激发后对分子间弱相互作用力的影响。本论文主要包括以下三部分:1.本文使用含时密度泛函理论(TDDFT)研究了甲醛单体及其与碱金属离子的复合物的电子激发态。使用TDDFT方法计算了几个单重态和三重激发态的垂直跃迁能量,第一单重态S_1和第一三重激发态T1的绝热跃迁能,甲醛及其复合物基态S_0态、S_1态和T1态的绝热几何形状和振动频率,在TDDFT水平下计算的CH_2O单体的数据比CIS方法更接近实验值。S_1和T1激发态中的非线性C=O…M+相互作用弱于基态中的线性相互作用。在S_0和S_1两态中,由于甲醛分子与金属离子之间形成弱相互作用力导致C=O键伸长,并且其伸缩振动频率红移;但在T1电子激发态的复合物中,C=O键缩短,其频率蓝移。2.本文使用含时密度泛函(TDDFT)方法,在B3LYP/6-311++G(d,p)水平下计算了激发态异烟肼与甲醛复合物(INH-CH_2O)的体系。INH-CH_2O复合物形成了两个分子间氢键,本文重点探讨了电子激发对复合物中两个氢键的不同影响。分析结果表明,INH分子与CH_2O分子间形成的氢键HB1在激发态时强度增强,HB2在发生电子激发时减弱甚至断裂。红外光谱分析显示由于异烟肼与甲醛形成了分子间氢键,使得C=O、C-H和N-H键的伸缩振动频率发生红移。由于发生电子激发,INH-CH_2O复合物中HB1相对应的C=O和H-C键发生红移,HB2相对应的C=O键发生红移而N-H键伸缩振动频率发生蓝移。3.本文用含时密度泛函(TDDFT)理论,对激发态异烟肼与甲醇复合物(INH-MeOH)的体系进行理论研究。在B3LYP/6-311++G*的水平下计算了分子单体和两种构型INH-MeOH复合物的几何结构、振动频率、电子光谱。构型1复合物中的HB1在电子激发后成键增强,而HB2成键减弱;构型2复合物中形成的两个分子间氢键C=O…H-C在S_1和T1状态下增强。两种构型复合物的S_1态、T1态是局域激发,其中INH分子被激发,MeOH分子仍处于基态。S_0→S_1和S_0→T1电子激发主要导致异烟肼中C=O键的频率有较大红移。
[Abstract]:Intermolecular interactions play a very important role in many physical and chemical and biological processes. In recent years, it has been found that the supermolecules of the excited state have special properties in the photophysical and photochemical processes. In this paper, a theoretical study on the three systems of the excited state complex (3) of the excited state complex (3) of the (1) formaldehyde and the alkali metal ions and the excited state complex (3) of the methanol is studied by the density functional theory and the time-density functional theory. The weak interaction force between the methanol and the alkali metal ion, the isosmotic and the organic small molecule and the key-forming nature of the weak bond of the excited state are analyzed by means of different methods. The effect of the formation of the weak interaction force on the monomer and the effect of the electron excitation on the weak interaction force of the molecule are also systematically analyzed. The thesis mainly includes the following three parts:1. In this paper, the electron excited state of the formaldehyde monomer and its complex with the alkali metal ion is studied by using the time-density functional theory (TDDFT). The adiabatic transition energy, the adiabatic transition energy of the first triplet state S _ 1 and the first triplet excited state T1, the adiabatic transition energy of the first singlet state S _ 1 and the first triplet excited state T1, the adiabatic geometrical shape and the vibration frequency of the S _ 0 state, the S _ 1 state and the T1 state of the first triplet state S _ 1 and the first triplet excited state T1 are calculated by using the TDDFT method, The data of the CH _ 2O monomer calculated at the TDDFT level is closer to the experimental value than the CIS method. Nonlinear C = O... in the excited states of S _ 1 and T1. The M + interaction is weaker than the linear interaction in the ground state. In the S _ 0 and S _ 1 states, due to the weak interaction force between the formaldehyde molecule and the metal ion, the C = O bond is elongated, and the telescopic vibration frequency is red; but in the complex of the T1 electron excited state, the C = O bond is shortened and the frequency of the C = O bond is blue. In this paper, we use the time-density functional (TDDFT) method to calculate the system of the excited-state isosmotic and formaldehyde complex (INH-CH _ 2O) at the B3LYP/6-311 ++ G (d, p) level. The two intermolecular hydrogen bonds are formed by the INH-CH _ 2O complex, and the different effects of the electron excitation on the two hydrogen bonds in the complex are discussed. The results show that the hydrogen bond HB1 formed between the INH molecule and the CH _ 2O molecule is enhanced in the excited state, and the HB2 is weakened or even broken when the electron excitation occurs. The infrared spectrum analysis shows that the expansion vibration frequency of C = O, C-H and N-H bonds is redshift due to the formation of intermolecular hydrogen bonds with the isosmotic and the formaldehyde. The C = O and H-C bonds corresponding to HB1 in the INH-CH _ 2O complex have a red shift due to the occurrence of the electron excitation, and the C = O bond corresponding to the HB2 is red, and the frequency of the N-H bond expansion vibration is blue shift. In this paper, the theory of time-density functional (TDDFT) is used to study the system of the excited-state isosmotic and methanol complex (INH-MeOH). The geometric structure, the vibration frequency and the electron spectrum of the molecular monomer and the two configurations of the INH-MeOH complex are calculated at the B3LYP/6-311 ++ G * level. The HB1 in the complex of the configuration 1 is enhanced after the electron excitation, while the HB2 bond is weakened; the two intermolecular hydrogen bonds formed in the configuration 2 complex are C = O... H-C is enhanced in the S _ 1 and T1 states. In the S _ 1 state of the two configuration complexes, the T1 state is a local excitation, in which the INH molecules are excited and the MeOH molecules are still in the ground state. The E-excitation of S _ 0-S _ 1 and S _ 0-T1 mainly resulted in a large red shift in the frequency of C = O bond in the isosmograph.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
本文编号：2501234
[Abstract]:Intermolecular interactions play a very important role in many physical and chemical and biological processes. In recent years, it has been found that the supermolecules of the excited state have special properties in the photophysical and photochemical processes. In this paper, a theoretical study on the three systems of the excited state complex (3) of the excited state complex (3) of the (1) formaldehyde and the alkali metal ions and the excited state complex (3) of the methanol is studied by the density functional theory and the time-density functional theory. The weak interaction force between the methanol and the alkali metal ion, the isosmotic and the organic small molecule and the key-forming nature of the weak bond of the excited state are analyzed by means of different methods. The effect of the formation of the weak interaction force on the monomer and the effect of the electron excitation on the weak interaction force of the molecule are also systematically analyzed. The thesis mainly includes the following three parts:1. In this paper, the electron excited state of the formaldehyde monomer and its complex with the alkali metal ion is studied by using the time-density functional theory (TDDFT). The adiabatic transition energy, the adiabatic transition energy of the first triplet state S _ 1 and the first triplet excited state T1, the adiabatic transition energy of the first singlet state S _ 1 and the first triplet excited state T1, the adiabatic geometrical shape and the vibration frequency of the S _ 0 state, the S _ 1 state and the T1 state of the first triplet state S _ 1 and the first triplet excited state T1 are calculated by using the TDDFT method, The data of the CH _ 2O monomer calculated at the TDDFT level is closer to the experimental value than the CIS method. Nonlinear C = O... in the excited states of S _ 1 and T1. The M + interaction is weaker than the linear interaction in the ground state. In the S _ 0 and S _ 1 states, due to the weak interaction force between the formaldehyde molecule and the metal ion, the C = O bond is elongated, and the telescopic vibration frequency is red; but in the complex of the T1 electron excited state, the C = O bond is shortened and the frequency of the C = O bond is blue. In this paper, we use the time-density functional (TDDFT) method to calculate the system of the excited-state isosmotic and formaldehyde complex (INH-CH _ 2O) at the B3LYP/6-311 ++ G (d, p) level. The two intermolecular hydrogen bonds are formed by the INH-CH _ 2O complex, and the different effects of the electron excitation on the two hydrogen bonds in the complex are discussed. The results show that the hydrogen bond HB1 formed between the INH molecule and the CH _ 2O molecule is enhanced in the excited state, and the HB2 is weakened or even broken when the electron excitation occurs. The infrared spectrum analysis shows that the expansion vibration frequency of C = O, C-H and N-H bonds is redshift due to the formation of intermolecular hydrogen bonds with the isosmotic and the formaldehyde. The C = O and H-C bonds corresponding to HB1 in the INH-CH _ 2O complex have a red shift due to the occurrence of the electron excitation, and the C = O bond corresponding to the HB2 is red, and the frequency of the N-H bond expansion vibration is blue shift. In this paper, the theory of time-density functional (TDDFT) is used to study the system of the excited-state isosmotic and methanol complex (INH-MeOH). The geometric structure, the vibration frequency and the electron spectrum of the molecular monomer and the two configurations of the INH-MeOH complex are calculated at the B3LYP/6-311 ++ G * level. The HB1 in the complex of the configuration 1 is enhanced after the electron excitation, while the HB2 bond is weakened; the two intermolecular hydrogen bonds formed in the configuration 2 complex are C = O... H-C is enhanced in the S _ 1 and T1 states. In the S _ 1 state of the two configuration complexes, the T1 state is a local excitation, in which the INH molecules are excited and the MeOH molecules are still in the ground state. The E-excitation of S _ 0-S _ 1 and S _ 0-T1 mainly resulted in a large red shift in the frequency of C = O bond in the isosmograph.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
【参考文献】
相关期刊论文 前2条
1 杨国强;;我国光化学研究的进展及展望[J];化学通报;2011年07期
2 刘丽君,郑行望,章竹君;电化学发光分析法测定异烟肼[J];分析化学;2003年09期
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