Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach
The nonlinear optical (NLO) characteristics exhibited by organic compounds hold significant value in the realm of photonics and optoelectronics applications. Herein, the Density Functional Theory method at MPW1PW91/6-311G (d,p) functional was utilized to evaluate the electronic and NLO behavior of n...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-11-01
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| Series: | Journal of Saudi Chemical Society |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S1319610323001710 |
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| author | Iqra Shafiq Romaisa Zahid Khalid Mahmood Muhammad Adnan Asgha Tansir Ahamad Sarfraz Ahmed Suvash Chandra Ojha |
| author_facet | Iqra Shafiq Romaisa Zahid Khalid Mahmood Muhammad Adnan Asgha Tansir Ahamad Sarfraz Ahmed Suvash Chandra Ojha |
| author_sort | Iqra Shafiq |
| collection | DOAJ |
| description | The nonlinear optical (NLO) characteristics exhibited by organic compounds hold significant value in the realm of photonics and optoelectronics applications. Herein, the Density Functional Theory method at MPW1PW91/6-311G (d,p) functional was utilized to evaluate the electronic and NLO behavior of novel compounds i.e., MTPBR1 having A-π-D-π-A and MTPBD2-MTPBD9 with D1-π-D2-π-A configurations. Quantum chemical computations revealed that structural tailoring of all the designed chromophores demonstrate reduced bandgaps with greater absorption properties than MTPBR1. The efficacy of charge transfer from the donor to the acceptor through a spacer was investigated using frontier molecular orbitals calculations. These calculations were substantiated by analyses of density of states and transition density matrices. Natural bonding orbitals indicated molecular stability in designed molecules due to hyper-conjugative interactions and extended conjugation. Among all the derivatives, MTPBD8 exhibited the lowest energy bandgap (1.891 eV) with bathochromic shift of 723.868 nm in chloroform and 546.688 nm in gaseous phase, and the highest global softness of 0.529 eV−1. MTPBD5 displayed the highest dipole moment (µtot) at 22.815 D. MTPBD2, MTPBD3, MTPBD5 and MTPBD8 demonstrated consistent linear polarizability 〈α〉 at 3.4 × 10−22 esu. Notably, MTPBD8 calculated the highest first and second hyperpolarizability (βtot, γtot) at 9.6 × 10–27 and 4.302 × 10−32 esu, respectively. To conclude, the novel chromophores, particularly MTPBD8, showed remarkable NLO properties, demonstrating their potential use in advanced nonlinear optical devices. |
| first_indexed | 2024-03-08T20:12:09Z |
| format | Article |
| id | doaj.art-7e2ed85195f449b5bb1a7e5678d3451e |
| institution | Directory Open Access Journal |
| issn | 1319-6103 |
| language | English |
| last_indexed | 2024-03-08T20:12:09Z |
| publishDate | 2023-11-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Journal of Saudi Chemical Society |
| spelling | doaj.art-7e2ed85195f449b5bb1a7e5678d3451e2023-12-23T05:20:14ZengElsevierJournal of Saudi Chemical Society1319-61032023-11-01276101767Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approachIqra Shafiq0Romaisa Zahid1Khalid Mahmood2Muhammad Adnan Asgha3Tansir Ahamad4Sarfraz Ahmed5Suvash Chandra Ojha6Institute of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan; Centre for Theoretical and Computational Research, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, PakistanInstitute of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan; Centre for Theoretical and Computational Research, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, PakistanInstitute of Chemical Sciences, Bahauddin Zakariya University, PakistanDepartment of Chemistry, Division of Science and Technology, University of Education Lahore, Pakistan; Corresponding authors.Department of Chemistry, College of Science, King Saud University, Saudi ArabiaWellman Center for Photomedicine, Harvard Medical School, Massachusetts General Hospital, Boston, MA 02114, United StatesDepartment of Infectious Diseases, The Affiliated Hospital of Southwest Medical University, Luzhou 646000, China; Corresponding authors.The nonlinear optical (NLO) characteristics exhibited by organic compounds hold significant value in the realm of photonics and optoelectronics applications. Herein, the Density Functional Theory method at MPW1PW91/6-311G (d,p) functional was utilized to evaluate the electronic and NLO behavior of novel compounds i.e., MTPBR1 having A-π-D-π-A and MTPBD2-MTPBD9 with D1-π-D2-π-A configurations. Quantum chemical computations revealed that structural tailoring of all the designed chromophores demonstrate reduced bandgaps with greater absorption properties than MTPBR1. The efficacy of charge transfer from the donor to the acceptor through a spacer was investigated using frontier molecular orbitals calculations. These calculations were substantiated by analyses of density of states and transition density matrices. Natural bonding orbitals indicated molecular stability in designed molecules due to hyper-conjugative interactions and extended conjugation. Among all the derivatives, MTPBD8 exhibited the lowest energy bandgap (1.891 eV) with bathochromic shift of 723.868 nm in chloroform and 546.688 nm in gaseous phase, and the highest global softness of 0.529 eV−1. MTPBD5 displayed the highest dipole moment (µtot) at 22.815 D. MTPBD2, MTPBD3, MTPBD5 and MTPBD8 demonstrated consistent linear polarizability 〈α〉 at 3.4 × 10−22 esu. Notably, MTPBD8 calculated the highest first and second hyperpolarizability (βtot, γtot) at 9.6 × 10–27 and 4.302 × 10−32 esu, respectively. To conclude, the novel chromophores, particularly MTPBD8, showed remarkable NLO properties, demonstrating their potential use in advanced nonlinear optical devices.http://www.sciencedirect.com/science/article/pii/S1319610323001710Non-fullereneQuantum chemical calculationsDFT/TD-DFTHyperpolarizabilityFMO |
| spellingShingle | Iqra Shafiq Romaisa Zahid Khalid Mahmood Muhammad Adnan Asgha Tansir Ahamad Sarfraz Ahmed Suvash Chandra Ojha Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach Journal of Saudi Chemical Society Non-fullerene Quantum chemical calculations DFT/TD-DFT Hyperpolarizability FMO |
| title | Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach |
| title_full | Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach |
| title_fullStr | Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach |
| title_full_unstemmed | Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach |
| title_short | Introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores: A quantum chemical approach |
| title_sort | introducing the various electron withdrawing functions in trigging the optical nonlinearity of benzodithiophene based chromophores a quantum chemical approach |
| topic | Non-fullerene Quantum chemical calculations DFT/TD-DFT Hyperpolarizability FMO |
| url | http://www.sciencedirect.com/science/article/pii/S1319610323001710 |
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