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Mekong Delta Natural Science Conference
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Nguyen, D. H., Pham, V. N., & Dang, M. T. (2025). Investigate the stability and opto-electronic properties of carbazole and its derivatives via quantum-chemical calculations. Dong Thap University Journal of Science, 14(04S), 480-494. https://doi.org/10.52714/dthu.14.04S.2025.1616
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Investigate the stability and opto-electronic properties of carbazole and its derivatives via quantum-chemical calculations
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Abstract
Nghiên cứu này khảo sát carbazole (a) và bốn dẫn xuất (b–e) ở mức DFT/TD-DFT nhằm làm rõ mối liên hệ cấu trúc và tính chất điện tử. Hình học ở trạng thái cơ bản Singlet (S0) được tối ưu bằng TPSS/6-311++G(d,p) (không có tần số ảo), còn ở trạng thái Triplet (T1)và các loài vỏ mở dùng UTPSS cùng bộ cơ sở tương ứng; phổ hấp thụ được mô phỏng bằng TD-DFT. Kết quả cho thấy nhóm dono –acceptor và vị trí gắn (2,7 so với 3,6; thay thế N-9 bằng Cl) đã điều chỉnh mạnh mẽ mức HOMO/LUMO, năng lượng kích thích ES1, ET1 và chênh lệch singlet–triplet (ΔES–T). Hai xu hướng nổi bật: Thứ nhất, khi gắn nhóm thế tại ví trí 3,6 trên khung carbazole để tạo hệ D–π–A (chất c) thì sẽ làm giảm ΔES–T xuống 0,58 eV và gây dịch chuyển đỏ mạnh; Thứ hai, nhóm thế Cl có thể làm suy giảm độ liên hợp và chuyển điện tích nội phân tử ICT (chất e), trong khi chất d vẫn hấp thụ ở vùng khả kiến (~420 nm) với cường độ tăng. Những kết quả này gợi ý chiến lược tối ưu hóa vị trí và loại nhóm thế trên khung carbazole cho các ứng dụng quang điện tử.
Keywords
Carbazole, DFT, TD-DFT, HOMO/LUMO, ES1/ET1, ΔES–T, UV-Vis
Article Details
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
References
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Lakhera, S., Devlal, K., Ghosh, A., Chowdhury, P., & Rana, M. (2022). Modelling the DFT structural and reactivity study of feverfew and evaluation of its potential antiviral activity against COVID-19 using molecular docking and MD simulations. Chemical Papers, 76(5), 2759-2776. https://doi.org/10.1007/s11696-022-02067-6
Lakhera, S., Rana, M., & Devlal, K. (2022). Theoretical study on spectral and optical properties of essential amino acids: a comparative study. Opt. Quantum Electron., 54(11), 714. https://doi.org/10.1007/s11082-022-04118-4
Lakhera, S., Rana, M., Devlal, K., Dhuliya, V., & Pandey, N. (2023). Non-linear optical behavior of gold and silver clusters adsorbed on 2, 9-Dimethylquinacridone. Optik, 286, 170983. https://doi.org/10.1016/j.ijleo.2023.170983
Lee, C., Yang, W., & Parr, R. G. (1988). Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical review B, 37(2), 785. https://doi.org/10.1103/PhysRevB.37.785
Meerholz, K., Volodin, B., Sandalphon, Kippelen, B., & Peyghambarian, N. (1994). A photorefractive polymer with high optical gain and diffraction efficiency near 100%. Nature, 371(6497), 497-500. https://doi.org/10.1038/371497a0
Rana, M., & Chowdhury, P. (2020). Nonlinear optical responses of organic based indole derivative: an experimental and computational study. Materials Today: Proceedings, 28, 241-245. https://doi.org/10.1016/j.matpr.2020.01.598
Rogers, C. U., & Corson, B. (1947). One-Step Synthesis of 1, 2, 3, 4-Tetrahydrocarbazole and 1, 2-Benzo-3, 4-dihydrocarbazole. Journal of the American Chemical Society, 69(11), 2910-2911. https://doi.org/10.1021/ja01203a506
Shi, H.-p., Cheng, Y., Jing, W.-j., Chao, J.-B., Fang, L., Dong, X., & Dong, C. (2010). Experimental and theoretical study of a new carbazole derivative having terminal benzimidazole rings. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 75(2), 525-532. https://doi.org/10.1016/j.saa.2009.11.003
Tao, J., Perdew, J. P., Staroverov, V. N., & Scuseria, G. E. (2003). Climbing the density functional ladder: Nonempirical meta–generalized gradient approximation designed for molecules and solids. Physical review letters, 91(14), 146401. https://doi.org/10.1103/PhysRevLett.91.146401
Barone, V., Bencini, A., & Fantucci, P. (2002). Recent advances in density functional methods (Vol. 1). World Scientific. https://doi.org/10.1142/4865
Becke, A. D. (1993). Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 98(7), 5648-5652. https://doi.org/10.1063/1.464913
Bernardo, G., Charas, A., & Morgado, J. (2010). Luminescence properties of poly (9, 9-dioctylfluorene)/polyvinylcarbazole blends: Role of composition on the emission colour stability and electroluminescence efficiency. Journal of Physics and Chemistry of Solids, 71(3), 340-345. https://doi.org/10.1016/j.jpcs.2009.12.087
Bingul, M., Şenkuytu, E., Saglam, M. F., Boga, M., Kandemir, H., & Sengul, I. F. (2019). Synthesis, photophysical and antioxidant properties of carbazole-based bis-thiosemicarbazones. Research on Chemical Intermediates, 45(9). https://doi.org/10.1007/s11164-019-03844-x
Davidge, H. (1959). Poly‐N‐vinylcarbazole. I. Preparation of N‐vinyl‐carbazole. Journal of Applied Chemistry, 9(4), 241-246. https://doi.org/10.1002/jctb.5010090408
Frisch, M., Trucks, G., Schlegel, H., Scuseria, G., Robb, M., Cheeseman, J., Scalmani, G., Barone, V., Petersson, G., & Nakatsuji, H. (2016). Gaussian 16, Gaussian 16 Revision C. 01. Gaussian Inc., Wallingford, CT.
Garza, A. J., Osman, O. I., Wazzan, N. A., Khan, S. B., Asiri, A. M., & Scuseria, G. E. (2014). A computational study of the nonlinear optical properties of carbazole derivatives: theory refines experiment. Theoretical Chemistry Accounts, 133(4), 1458. https://doi.org/10.1007/s00214-014-1458-9
González-Ruiz, V., Cores, Á., Caja, M. M., Sridharan, V., Villacampa, M., Martín, M. A., Olives, A. I., & Menéndez, J. C. (2022). Fluorescence sensors based on hydroxycarbazole for the determination of neurodegeneration-related halide anions. Biosensors, 12(3), 175. https://doi.org/10.3390/bios12030175
Gross, a. E., Dobson, J., & Petersilka, M. (2005). Density functional theory of time-dependent phenomena. In Density Functional Theory II: Relativistic and Time Dependent Extensions (pp. 81-172). Springer. https://doi.org/10.1007/BFb0016643
Guo, X., Baumgarten, M., & Müllen, K. (2013). Designing π-conjugated polymers for organic electronics. Progress in Polymer Science, 38(12), 1832-1908. https://doi.org/10.1016/j.progpolymsci.2013.09.005
Hehre, W. J., Ditchfield, R., & Pople, J. A. (1972). Self—consistent molecular orbital methods. XII. Further extensions of Gaussian—type basis sets for use in molecular orbital studies of organic molecules. The Journal of Chemical Physics, 56(5), 2257-2261. https://doi.org/10.1063/1.1677527
Hlel, A., Mabrouk, A., Chemek, M., Khalifa, I. B., & Alimi, K. (2015). A DFT study of charge-transfer and opto-electronic properties of some new materials involving carbazole units. Computational Condensed Matter, 3, 30-40. https://doi.org/10.1016/j.cocom.2015.02.001
Hohenberg, P., & Kohn, W. (1964). Inhomogeneous electron gas. Physical review, 136(3B), B864. https://doi.org/10.1103/PhysRev.136.B864
Huong, V. T. T., Tai, T. B., & Nguyen, M. T. (2015). Design of novel tetra-hetero [8] circulenes: a theoretical study of electronic structure and charge transport characteristics. RSC Advances, 5(31), 24167-24174. https://doi.org/10.1039/C4RA16485G
Jacquemin, D., Wathelet, V., Perpete, E. A., & Adamo, C. (2009). Extensive TD-DFT benchmark: singlet-excited states of organic molecules. Journal of Chemical Theory and Computation, 5(9), 2420-2435. https://doi.org/10.1021/ct900298e
Kohn, W., & Sham, L. J. (1965). Self-consistent equations including exchange and correlation effects. Physical review, 140(4A), A1133. https://doi.org/10.1103/PhysRev.140.A1133
Lakhera, S., Devlal, K., Ghosh, A., Chowdhury, P., & Rana, M. (2022). Modelling the DFT structural and reactivity study of feverfew and evaluation of its potential antiviral activity against COVID-19 using molecular docking and MD simulations. Chemical Papers, 76(5), 2759-2776. https://doi.org/10.1007/s11696-022-02067-6
Lakhera, S., Rana, M., & Devlal, K. (2022). Theoretical study on spectral and optical properties of essential amino acids: a comparative study. Opt. Quantum Electron., 54(11), 714. https://doi.org/10.1007/s11082-022-04118-4
Lakhera, S., Rana, M., Devlal, K., Dhuliya, V., & Pandey, N. (2023). Non-linear optical behavior of gold and silver clusters adsorbed on 2, 9-Dimethylquinacridone. Optik, 286, 170983. https://doi.org/10.1016/j.ijleo.2023.170983
Lee, C., Yang, W., & Parr, R. G. (1988). Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical review B, 37(2), 785. https://doi.org/10.1103/PhysRevB.37.785
Meerholz, K., Volodin, B., Sandalphon, Kippelen, B., & Peyghambarian, N. (1994). A photorefractive polymer with high optical gain and diffraction efficiency near 100%. Nature, 371(6497), 497-500. https://doi.org/10.1038/371497a0
Rana, M., & Chowdhury, P. (2020). Nonlinear optical responses of organic based indole derivative: an experimental and computational study. Materials Today: Proceedings, 28, 241-245. https://doi.org/10.1016/j.matpr.2020.01.598
Rogers, C. U., & Corson, B. (1947). One-Step Synthesis of 1, 2, 3, 4-Tetrahydrocarbazole and 1, 2-Benzo-3, 4-dihydrocarbazole. Journal of the American Chemical Society, 69(11), 2910-2911. https://doi.org/10.1021/ja01203a506
Shi, H.-p., Cheng, Y., Jing, W.-j., Chao, J.-B., Fang, L., Dong, X., & Dong, C. (2010). Experimental and theoretical study of a new carbazole derivative having terminal benzimidazole rings. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 75(2), 525-532. https://doi.org/10.1016/j.saa.2009.11.003
Tao, J., Perdew, J. P., Staroverov, V. N., & Scuseria, G. E. (2003). Climbing the density functional ladder: Nonempirical meta–generalized gradient approximation designed for molecules and solids. Physical review letters, 91(14), 146401. https://doi.org/10.1103/PhysRevLett.91.146401
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