几类重要小分子和自由基激发态光解离反应机理的理论研究
摘要
光解离反应是光化学反应中的重要形式之一,在很多领域发挥着独特的作用。本文采用高水平的完全活化空间自洽场方法(CASSCF)和多参考态二级微扰理论(CASPT2),研究了几类重要小分子和自由基的光解离反应动力学。主要贡献如下:一、以乙烯酮分子为研究对象,建立了体系详细的基态和激发态势能面,并且确定了发生非绝热相互作用的势能面的交叉区域,揭示了乙烯酮分子被激发到最低的里得堡态(~1B_1)上以后发生光解离反应的机理。二、以HCNN自由基为研究对象,构建了HCNN的四重激发态(a|~)~4A"的详细势能面,为实验上推测的HCNN的光解离机理提供了有力的支持。三、研究了潜在的星际分子PC_3O的各种双重态异构体的几何结构,能量,光谱及稳定性,找到了四种动力学上最稳定的异构体,为将来实验室和星际探测提供理论指导。
Photodissociation reaction, as one of the most important photochemistry reactions, provides significant theoretical foundation for the study of life and environment sciences. It also plays a special role in many fields, such as new materials, new energy sources, and new technique for information dispatch. In the present paper, high-level quantum chemistry methods are performed to further explore the ground and excited states properties, as well as the photodissociation reaction mechanism of some molecules or radicals, which have attracted considerable attention in the environment, atmospheric process, and interstellar chemistry. It is expected to be informative for the experiment investigations in the future. The main contributions are as follows:
1. In the present study, an attempt is made to reveal the main mechanism of photodissociation on the lowest-lying Rydberg state ~1B_1 of ketene, referred to as the second singlet excited state S_2, by means of the complete active space self-consistent field (CASSCF) and second-order multiconfigurational perturbation theory methods (CASPT2). The located S_2/S_1/T_1 three-surface intersection plays an important role in the dissociation process. It is shown that the intersection permits an efficient internal conversion from S_2 to S_1 state, but prohibits the intersystem crossing from S_2 to T1 state because of the small spin-orbital coupling interaction. The main photodissociation process could be described as follows: after one photon absorption to the S_2 state, ketene preferentially relaxes to the minimum S_2_C_(2v), and undergoes a transition state S_2_TS with small potential barrier along the Cs-Ι(out-of-plane bent) symmetry, and passes through the S_2/S_1/T_1 intersection to reach S_1 surface, then arrives at the transition state S_1_TS along the minimum energy path. As is well known, S_1→S_0 internal conversion around the Franck-Condon region is expected to be very efficient, and eventually the hot S0 molecule has accumulated enough energy to yield the CH_2 ((a|~)~1A_1) and CO ( X|~~1Σ~+) products. Our conclusion supported the recent experiment findings, and also provides some necessary details for the photodissociaion mechanism. 2. Complete active space self-consistent field (CASSCF) and second-order multiconfigurational perturbation theory methods (CASPT2) have been performed to investigate the quartet excited state (a|~)~4A" potential energy surface of HCNN radical. Two located minima, with respective cis and trans structures, could easily dissociate to CH ((a|~)~4Σ~-) and N_2 ( (X|~)~1Σ_g~+) products with similar barrier of about 16.0 kcal/mol. In addition, four minimum energy crossing points on a surface of intersection between (a|~)~4A" and X (X= (X|~)~2A" and (A|~)~2A') states are located near to the minima. However, the intersystem crossing (a|~)~4A"→X is weak due to the vanishingly small spin-orbit interaction. It further indicates that the direct dissociation on the (a|~)~4A" state is more favored. This information combined with the comparison with isoelectronic HCCO provides an indirect support to recent experimental proposal of photodissociation mechanism of HCNN,i.e., internal conversion to one or both of the (X|~)~2A" and (A|~)~2A' states, instead of intersystem crossing, is involved in the photodissociation mechanism of HCNN radical. 3. DFT/B3LYP/6-311G(d) and CCSD(T)/6-311G(2d) single-point calculations are carried out for exploring the doublet potential energy surface (PES) of PC_3O, a molecule of potential interest in interstellar chemistry. A total of 29 minima connected by 65 interconversion transition states are located. The structures of the most relevant isomers and transition states are further optimized at the QCISD level followed by CCSD(T) single-point energy calculations. At the CCSD(T)/6-311G(2df)//QCISD/6-311G(d)+ZPVE level, the global minimum is the quasi-linear structure PCCCO 1 (0.0 kcal/mol) with a great kinetic stability of 47.9 kcal/mol, and the cumulenic form features largely in its resonance structures. Moreover, the chainlike isomer OPCCC 3 (64.5) and five-membered-ring species cPCCCO 19 (77.8) possess considerable kinetic stability of about 18.0 kcal/mol. All of these three isomers are very promising candidates for future experimental and astrophysical detection. Additionally, a three-membered-ring isomer CC-cCOP 10 (69.6) has slightly lower kinetic stability of around 15 kcal/mol and also may be experimentally observable. Possible formation mechanisms of the four stable isomers in interstellar space are discussed. The present research is the first attempt to study the isomerization and dissociation mechanisms of PC_nO series. The predicted spectroscopic properties, including harmonic vibrational frequencies, dipole moments and rotational constants for the relevant isomers, are expected to be informative for the identification of PC_3O in laboratory and interstellar medium.
Photodissociation reaction, as one of the most important photochemistry reactions, provides significant theoretical foundation for the study of life and environment sciences. It also plays a special role in many fields, such as new materials, new energy sources, and new technique for information dispatch. In the present paper, high-level quantum chemistry methods are performed to further explore the ground and excited states properties, as well as the photodissociation reaction mechanism of some molecules or radicals, which have attracted considerable attention in the environment, atmospheric process, and interstellar chemistry. It is expected to be informative for the experiment investigations in the future. The main contributions are as follows:
1. In the present study, an attempt is made to reveal the main mechanism of photodissociation on the lowest-lying Rydberg state ~1B_1 of ketene, referred to as the second singlet excited state S_2, by means of the complete active space self-consistent field (CASSCF) and second-order multiconfigurational perturbation theory methods (CASPT2). The located S_2/S_1/T_1 three-surface intersection plays an important role in the dissociation process. It is shown that the intersection permits an efficient internal conversion from S_2 to S_1 state, but prohibits the intersystem crossing from S_2 to T1 state because of the small spin-orbital coupling interaction. The main photodissociation process could be described as follows: after one photon absorption to the S_2 state, ketene preferentially relaxes to the minimum S_2_C_(2v), and undergoes a transition state S_2_TS with small potential barrier along the Cs-Ι(out-of-plane bent) symmetry, and passes through the S_2/S_1/T_1 intersection to reach S_1 surface, then arrives at the transition state S_1_TS along the minimum energy path. As is well known, S_1→S_0 internal conversion around the Franck-Condon region is expected to be very efficient, and eventually the hot S0 molecule has accumulated enough energy to yield the CH_2 ((a|~)~1A_1) and CO ( X|~~1Σ~+) products. Our conclusion supported the recent experiment findings, and also provides some necessary details for the photodissociaion mechanism. 2. Complete active space self-consistent field (CASSCF) and second-order multiconfigurational perturbation theory methods (CASPT2) have been performed to investigate the quartet excited state (a|~)~4A" potential energy surface of HCNN radical. Two located minima, with respective cis and trans structures, could easily dissociate to CH ((a|~)~4Σ~-) and N_2 ( (X|~)~1Σ_g~+) products with similar barrier of about 16.0 kcal/mol. In addition, four minimum energy crossing points on a surface of intersection between (a|~)~4A" and X (X= (X|~)~2A" and (A|~)~2A') states are located near to the minima. However, the intersystem crossing (a|~)~4A"→X is weak due to the vanishingly small spin-orbit interaction. It further indicates that the direct dissociation on the (a|~)~4A" state is more favored. This information combined with the comparison with isoelectronic HCCO provides an indirect support to recent experimental proposal of photodissociation mechanism of HCNN,i.e., internal conversion to one or both of the (X|~)~2A" and (A|~)~2A' states, instead of intersystem crossing, is involved in the photodissociation mechanism of HCNN radical. 3. DFT/B3LYP/6-311G(d) and CCSD(T)/6-311G(2d) single-point calculations are carried out for exploring the doublet potential energy surface (PES) of PC_3O, a molecule of potential interest in interstellar chemistry. A total of 29 minima connected by 65 interconversion transition states are located. The structures of the most relevant isomers and transition states are further optimized at the QCISD level followed by CCSD(T) single-point energy calculations. At the CCSD(T)/6-311G(2df)//QCISD/6-311G(d)+ZPVE level, the global minimum is the quasi-linear structure PCCCO 1 (0.0 kcal/mol) with a great kinetic stability of 47.9 kcal/mol, and the cumulenic form features largely in its resonance structures. Moreover, the chainlike isomer OPCCC 3 (64.5) and five-membered-ring species cPCCCO 19 (77.8) possess considerable kinetic stability of about 18.0 kcal/mol. All of these three isomers are very promising candidates for future experimental and astrophysical detection. Additionally, a three-membered-ring isomer CC-cCOP 10 (69.6) has slightly lower kinetic stability of around 15 kcal/mol and also may be experimentally observable. Possible formation mechanisms of the four stable isomers in interstellar space are discussed. The present research is the first attempt to study the isomerization and dissociation mechanisms of PC_nO series. The predicted spectroscopic properties, including harmonic vibrational frequencies, dipole moments and rotational constants for the relevant isomers, are expected to be informative for the identification of PC_3O in laboratory and interstellar medium.
引文
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