甲醛與堿金屬離子、異煙肼與有機小分子相互作用激發(fā)態(tài)的理論研究
發(fā)布時間：2019-06-17 20:10
【摘要】：分子間相互作用力在許多物理和化學、生物過程中具有十分重要的作用,在過去幾十年間引起了科研工作者們的廣泛關(guān)注。近年來,人們發(fā)現(xiàn)激發(fā)態(tài)的超分子在光物理和光化學過程中有著特殊的性質(zhì)。本文用密度泛函理論與含時密度泛函理論,對(1)甲醛與堿金屬離子的激發(fā)態(tài)復合物(2)異煙肼與甲醛的激發(fā)態(tài)復合物(3)異煙肼與甲醇的激發(fā)態(tài)復合物三個體系進行理論研究。文中利用不同的方法分析了甲醇與堿金屬離子、異煙肼與有機小分子之間的弱相互作用力、激發(fā)態(tài)弱鍵的成鍵本質(zhì),并系統(tǒng)地分析了分子間弱相互作用力形成后對單體的影響以及電子激發(fā)后對分子間弱相互作用力的影響。本論文主要包括以下三部分:1.本文使用含時密度泛函理論(TDDFT)研究了甲醛單體及其與堿金屬離子的復合物的電子激發(fā)態(tài)。使用TDDFT方法計算了幾個單重態(tài)和三重激發(fā)態(tài)的垂直躍遷能量,第一單重態(tài)S_1和第一三重激發(fā)態(tài)T1的絕熱躍遷能,甲醛及其復合物基態(tài)S_0態(tài)、S_1態(tài)和T1態(tài)的絕熱幾何形狀和振動頻率,在TDDFT水平下計算的CH_2O單體的數(shù)據(jù)比CIS方法更接近實驗值。S_1和T1激發(fā)態(tài)中的非線性C=O…M+相互作用弱于基態(tài)中的線性相互作用。在S_0和S_1兩態(tài)中,由于甲醛分子與金屬離子之間形成弱相互作用力導致C=O鍵伸長,并且其伸縮振動頻率紅移;但在T1電子激發(fā)態(tài)的復合物中,C=O鍵縮短,其頻率藍移。2.本文使用含時密度泛函(TDDFT)方法,在B3LYP/6-311++G(d,p)水平下計算了激發(fā)態(tài)異煙肼與甲醛復合物(INH-CH_2O)的體系。INH-CH_2O復合物形成了兩個分子間氫鍵,本文重點探討了電子激發(fā)對復合物中兩個氫鍵的不同影響。分析結(jié)果表明,INH分子與CH_2O分子間形成的氫鍵HB1在激發(fā)態(tài)時強度增強,HB2在發(fā)生電子激發(fā)時減弱甚至斷裂。紅外光譜分析顯示由于異煙肼與甲醛形成了分子間氫鍵,使得C=O、C-H和N-H鍵的伸縮振動頻率發(fā)生紅移。由于發(fā)生電子激發(fā),INH-CH_2O復合物中HB1相對應的C=O和H-C鍵發(fā)生紅移,HB2相對應的C=O鍵發(fā)生紅移而N-H鍵伸縮振動頻率發(fā)生藍移。3.本文用含時密度泛函(TDDFT)理論,對激發(fā)態(tài)異煙肼與甲醇復合物(INH-MeOH)的體系進行理論研究。在B3LYP/6-311++G*的水平下計算了分子單體和兩種構(gòu)型INH-MeOH復合物的幾何結(jié)構(gòu)、振動頻率、電子光譜。構(gòu)型1復合物中的HB1在電子激發(fā)后成鍵增強,而HB2成鍵減弱;構(gòu)型2復合物中形成的兩個分子間氫鍵C=O…H-C在S_1和T1狀態(tài)下增強。兩種構(gòu)型復合物的S_1態(tài)、T1態(tài)是局域激發(fā),其中INH分子被激發(fā),MeOH分子仍處于基態(tài)。S_0→S_1和S_0→T1電子激發(fā)主要導致異煙肼中C=O鍵的頻率有較大紅移。
[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.
【學位授予單位】：西南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.3
本文編號：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.
【學位授予單位】：西南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.3
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，本文編號：2501234
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