Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties

In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conforma...

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Main Authors: Bibi, Amna, Muhammad, Shabbir, UrRehman, Shafiq, Bibi, Shamsa, Bashir, Shahid, Ayub, Khurshid, Adnan, Muhammad, Khalid, Muhammad
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Published: American Chemical Society 2021
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spelling my.um.eprints.338912022-07-18T03:49:48Z http://eprints.um.edu.my/33891/ Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties Bibi, Amna Muhammad, Shabbir UrRehman, Shafiq Bibi, Shamsa Bashir, Shahid Ayub, Khurshid Adnan, Muhammad Khalid, Muhammad QD Chemistry In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (alpha(iso)) polarizability value of 603.1 X 10(-24) esu is shown by compound 7 which is similar to 12, similar to 16, similar to 9, similar to 11, similar to 10, and similar to 4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability <gamma > with an amplitude of 7607 x 10(-36) esu at the M06/6-311G** level of theory, which is similar to 521, similar to 505, similar to 38, similar to 884, similar to 185, and similar to 15 times more than that of compounds 1-6, respectively. The extensively larger <gamma > amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications. American Chemical Society 2021-09-28 Article PeerReviewed Bibi, Amna and Muhammad, Shabbir and UrRehman, Shafiq and Bibi, Shamsa and Bashir, Shahid and Ayub, Khurshid and Adnan, Muhammad and Khalid, Muhammad (2021) Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties. ACS Omega, 6 (38). pp. 24602-24613. ISSN 2470-1343, DOI https://doi.org/10.1021/acsomega.1c03218 <https://doi.org/10.1021/acsomega.1c03218>. 10.1021/acsomega.1c03218
institution Universiti Malaya
building UM Library
collection Institutional Repository
continent Asia
country Malaysia
content_provider Universiti Malaya
content_source UM Research Repository
url_provider http://eprints.um.edu.my/
topic QD Chemistry
spellingShingle QD Chemistry
Bibi, Amna
Muhammad, Shabbir
UrRehman, Shafiq
Bibi, Shamsa
Bashir, Shahid
Ayub, Khurshid
Adnan, Muhammad
Khalid, Muhammad
Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
description In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (alpha(iso)) polarizability value of 603.1 X 10(-24) esu is shown by compound 7 which is similar to 12, similar to 16, similar to 9, similar to 11, similar to 10, and similar to 4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability <gamma > with an amplitude of 7607 x 10(-36) esu at the M06/6-311G** level of theory, which is similar to 521, similar to 505, similar to 38, similar to 884, similar to 185, and similar to 15 times more than that of compounds 1-6, respectively. The extensively larger <gamma > amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.
format Article
author Bibi, Amna
Muhammad, Shabbir
UrRehman, Shafiq
Bibi, Shamsa
Bashir, Shahid
Ayub, Khurshid
Adnan, Muhammad
Khalid, Muhammad
author_facet Bibi, Amna
Muhammad, Shabbir
UrRehman, Shafiq
Bibi, Shamsa
Bashir, Shahid
Ayub, Khurshid
Adnan, Muhammad
Khalid, Muhammad
author_sort Bibi, Amna
title Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
title_short Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
title_full Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
title_fullStr Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
title_full_unstemmed Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
title_sort chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties
publisher American Chemical Society
publishDate 2021
url http://eprints.um.edu.my/33891/
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