Prediction Method for Optoelectronic Properties of Gallium Corrole-based Dye Sensitizers with Different Spatial Structures
Through density functional theory and time-containing density functional theory, the ground state and excited state properties of gallium carrotyl dye sensitizers were studied, and the problem of predicting the photoelectric performance of gallium carrotyl dye sensitizers in the prior art was solved, and rapid and accurate performance prediction and cost reduction were achieved.
Patent Information
- Application Number
- CN202111404517.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-11-24
- Publication Date
- 2025-07-04
- Estimated Expiration
- 2041-11-24
AI Technical Summary
The prior art is difficult to quickly and accurately predict the photoelectric properties of gallium-carrot-based dye sensitizers with different spatial structures, resulting in a long research and development cycle and high cost of dye-sensitized solar cells.
Density functional theory (DFT) and time-containing density functional theory (TD-DFT) were used to study the ground state and excited state properties of gallium carrotyl dye sensitizers. By constructing molecular models, structural optimization and charge transfer properties analysis were carried out, and gallium carrotyl dye sensitizers with excellent photoelectric properties were screened out.
It achieves rapid and accurate prediction of the photoelectric properties of gallium-carrot-based dye sensitizer, providing a theoretical basis for experiments, shortening the R&D cycle and reducing costs.
Smart Images
Figure CN114220495B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of dye-sensitized solar cells, and relates to a method for predicting the optoelectronic properties of gallium corrole-based dye sensitizers with different spatial structures. The method is characterized by designing a series of gallium corrole-based dye sensitizers with different spatial structures, and using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) to study their ground-state and excited-state properties, so as to theoretically predict the optoelectronic properties of gallium corrole-based dye sensitizers with different spatial structures. Background Art
[0002] Corrole and its derivatives have attracted great attention, and a large number of studies mainly focus on their photophysical properties. Many researchers have adjusted the substitution positions of substituents on the corrole ring to regulate the optoelectronic properties of some corrole compounds, thereby broadening their applications in different research fields. Solar energy is an important renewable resource, and the existing photovoltaic industry is an industry that utilizes solar energy. Among them, dye sensitizers are important components in photovoltaic devices. Therefore, if corrole can be used as the basic unit to design new solar dyes, it is expected to obtain solar dye cells with better optoelectronic properties. By using computer technology, molecules can be designed theoretically and their physicochemical properties can be studied, and molecules that meet the expectations can be screened out. Then, based on theoretical calculations as a reference, molecular synthesis experiments can be carried out, greatly reducing the workload and significantly shortening the R & D cycle of dye molecules, and developing dye sensitizers with low cost, environmental friendliness and excellent performance. Summary of the Invention
[0003] The purpose of the present invention is to provide a method for predicting the optoelectronic properties of gallium corrole-based dye sensitizers with different spatial structures, and to help design experimental methods from a theoretical perspective.
[0004] To achieve the above purpose, the technical solution adopted by the present invention is:
[0005] A method for predicting the optoelectronic properties of gallium corrole-based dye sensitizers with different spatial structures, and the prediction method is specifically carried out according to the following steps:
[0006] 1) Design a gallium corrole-based dye sensitizer based on the donor-π bridge-acceptor structure, and construct a molecular model of the dye sensitizer; use the Gaussian 09 software package to optimize the structure of the gallium corrole dye sensitizer in the gas phase, and compare all dye molecular structures and frontier molecular orbitals through density functional theory;
[0007] 2) Use the time-dependent density functional theory method to obtain the intramolecular charge transfer properties of the gallium corrole dye sensitizer molecule, and predict the properties of gallium corrole dye molecules with different spatial structures through the differences in intramolecular charge transfer properties;
[0008] 3) Based on the situations in steps 1) and 2), gallium corrole-based dye sensitizers with excellent optoelectronic properties are screened out.
[0009] Specifically, step (1) is to obtain the bond lengths and dihedral angles of gallium corrole dye sensitizer molecules through density functional theory, and analyze the influence of different spatial structures on the molecular structure.
[0010] Specifically, step (1) is to obtain the frontier orbital electron cloud density distribution and the energy level difference of HOMO-LUMO of gallium corrole dye sensitizer molecules through density functional theory; analyze the distributions of HOMO and LUMO in the donor group, corrole group, π-bridge and anchoring group.
[0011] Preferably, the density functional theory in step (1) is specifically the B3LYP method and the 6-311G(d,p) basis set in density functional theory.
[0012] Specifically, step (2) is to use time-dependent density functional theory and select the polarizable continuum model (PCM) to simulate the solvent environment; calculate the charge transfer length and transferred charge amount of gallium corrole dye sensitizer molecules in the ground state geometric optimization state after being excited, and analyze the intramolecular charge transfer situation.
[0013] Preferably, the time-dependent density functional theory is specifically the M06 method and the 6-311G(d,p) basis set in time-dependent density functional theory.
[0014] Preferably, the solvent is tetrahydrofuran.
[0015] The method of the present invention effectively utilizes the density functional theory method to optimize the molecular models of gallium corrole-based dye sensitizers with different spatial structures, and calculates the intramolecular charge transfer properties through the time-dependent density functional theory method. Compared with experiments, it can obtain output information such as the ground state molecular structure and intramolecular charge transfer more quickly and accurately, effectively avoiding the interference of other substances, and then predicting the properties of a series of dye molecules based on the theoretical values. The method of the present invention can predict the optoelectronic properties of gallium corrole-based dye sensitizer molecules with different spatial structures, providing a certain theoretical basis for experiments. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 Structural formulas of three gallium corrole dye molecules selected in the method of the present invention.
[0017] Figure 2 Charge density distributions of the frontier molecular orbitals of three gallium corrole dye molecules selected in the method of the present invention.
[0018] Figure 3 Energy level distribution diagrams of the frontier molecular orbitals of three gallium corrole dye molecules selected in the method of the present invention. DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
[0020] The present invention provides a method for predicting the optoelectronic properties of gallium corrole-based dye sensitizer molecules with different spatial structures by using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), which is specifically carried out according to the following steps:
[0021] 1) Model construction
[0022] Select the following three gallium corrole dye molecules (as Figure 1 shown) as the research objects. Use the GaussView program to construct the molecular structures of the above three gallium corrole dye molecules.
[0023] 2) Ground state structure optimization
[0024] Adopt the B3LYP method and the 6-311G(d,p) basis set to optimize the structures of the selected molecules in the gas phase environment. Extract the information of bond lengths and dihedral angles, list and compare them. From the bond length data in Table 1, different spatial structures have little effect on the bond lengths in gallium corrole dye molecules. From the dihedral angle data, gallium corrole dye molecules with different spatial structures all have good planarity. Obtain the frontier orbital electron density distribution maps (as Figure 2 shown) of the above gallium corrole dye molecules and the magnitudes of their HOMO-LUMO energy level differences (as Figure 3 and Table 2 shown) during the ground state structure optimization.
[0025] Table 1 Bond lengths and dihedral angles (°) of a series of gallium corrole dye molecules
[0026]
[0027]
[0028] Table 2 Frontier molecular orbital energies (eV) and energy level differences Eg (eV) of gallium corrole dye molecules
[0029]
[0030] From Figure 3 the calculation results, it can be seen that the HOMOs of dyes A, B, and C are almost distributed in the donor group and the corrole group, and are not affected by the change of the connection form. In contrast, the LUMO is mostly restricted in the donor group, the corrole group, the π-bridge, and the anchoring group. Although the donor-acceptor relative positions of the designed dye sensitizer molecules are different, the distributions of the HOMO and the LUMO are significantly similar. From Table 2, the HOMO-LUMO energy level difference in C is higher than that in both A and B.
[0031] 3) Intramolecular Charge Transfer Calculation
[0032] Using the M06 method and 6-311G(d,p) basis set in time-dependent density functional theory (TD-DFT), and choosing the polarized continuum model (PCM) to simulate the tetrahydrofuran solvent environment, the excited state calculation was carried out on the gallium corrole dye sensitizer molecule in the ground state geometric optimization state, and the intramolecular charge transfer analysis was carried out. As shown in Table 3. The charge transfer length (d CT ) and the transferred charge (q CT ) and other key parameters were used to quantitatively analyze the intramolecular charge transfer characteristics and are listed in Table 3. In the dye molecule, dye molecule B performs best in the key parameters q CT and d CT , indicating more efficient intramolecular charge transfer performance.
[0033] Table 3 d CT , q CT
[0034]
[0035] The method of the present invention uses DFT and TD-DFT calculations to study the geometric configuration, molecular orbital energy levels, and intramolecular charge transfer performance of gallium corrole-based dye sensitizer molecules with different spatial structures. It can be seen that the differences in the structural parameters such as bond lengths and dihedral angles and the electron cloud density distribution of gallium corrole-based dye sensitizer molecules with different spatial structures are not very large. Compared with dye molecules A and C, dye molecule B has better intramolecular charge transfer performance, which means that dye molecule B may have better optoelectronic properties and is a more suitable candidate as a dye for solar dye-sensitized cells.
Claims
1. A prediction method for the optoelectronic properties of gallium corrole-based dye sensitizers with different spatial structures, characterized in that, The prediction method is specifically carried out according to the following steps: 1) Design a gallium corrole-based dye sensitizer using the donor-π-bridge-acceptor structure and construct a molecular model of the dye sensitizer; optimize the structure of the gallium corrole dye sensitizer in the gas phase using the Gaussian 09 software package, and compare the structures and frontier molecular orbitals of all dye molecules through density functional theory; 2) Use the time-dependent density functional theory method to obtain the intramolecular charge transfer properties of the gallium corrole dye sensitizer molecule, and predict the properties of dye molecules with different spatial structures through the differences in intramolecular charge transfer properties; 3) Screen out gallium corrole-based dye sensitizers with excellent optoelectronic properties according to the situations in steps 1) and 2); The density functional theory described in step 1) is specifically the B3LYP method and the 6-311G(d,p) basis set in density functional theory; The time-dependent density functional theory described in step 2) is specifically the M06 method and the 6-311G(d,p) basis set in time-dependent density functional theory.
2. The prediction method for the optoelectronic properties of a gallium corrole-based dye sensitizer with different spatial structures according to claim 1, wherein: The comparison of the structures of all dye molecules through density functional theory described in step 1) specifically means obtaining the bond lengths and dihedral angles of the gallium corrole dye sensitizer molecule through density functional theory, and analyzing the influence of different spatial structures on the molecular structure.
3. The prediction method of the optoelectronic properties of gallium corrole-based dye sensitizers with different spatial structures according to claim 1, characterized in that: The comparison of the frontier molecular orbitals of all dye molecules through density functional theory described in step 1) specifically means obtaining the electron cloud density distribution of the frontier orbitals and the energy level difference between HOMO and LUMO of the gallium corrole dye sensitizer molecule through density functional theory; analyzing the distributions of HOMO and LUMO in the donor group, corrole group, π-bridge, and anchoring group.
4. The prediction method of the optoelectronic properties of a gallium corrole-based dye sensitizer with different spatial structures according to claim 1, characterized in that: Step 2) specifically means using the time-dependent density functional theory and selecting the polarized continuum model to simulate the solvent environment; calculating the charge transfer length and transferred charge amount of the gallium corrole dye sensitizer molecule in the ground state geometry optimization state after being excited, and analyzing the intramolecular charge transfer situation.
5. The prediction method for the optoelectronic properties of a gallium corrole-based dye sensitizer with different spatial structures according to claim 4, characterized in that: The solvent is tetrahydrofuran.