Sains Malaysiana 51(7)(2022): 2097-2118

http://doi.org/10.17576/jsm-2022-5107-13

DFT and CBS Study of Ethyl Acetate Conformers in the Neutral Hydrolysis

(Kajian DFT dan CBS terhadap Konformer Etil Asetat dalam Hidrolisis Neutral)

VERA KHOIRUNISA^1,2, FEBDIAN RUSYDI^3,4*, ROICHATUL MADINAH^4,5, HERMAWAN KRESNO DIPOJONO¹, FAOZAN AHMAD⁶, MUDASIR⁷, IRA PUSPITASARI^4,8 & AZIZAN AHMAD⁵

¹Department of Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung, Jl. Ganesha no. 10, Bandung 40132, Indonesia

²Engineering Physics Study Program Institut Teknologi Sumatera, Jl. Terusan Ryacudu Lampung Selatan 35365, Indonesia

³Department of Physics, Faculty of Science and Technology, Universitas Airlangga, Jl. Mulyorejo, Surabaya 60115, Indonesia

⁴Research Center for Quantum Engineering Design, Faculty of Science and Technology Universitas Airlangga, Jl. Mulyorejo, Surabaya 60115, Indonesia

⁵Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

⁶Department of Physics, Faculty of Mathematics and Science, Institut Pertanian Bogor, Bogor 16680, Indonesia

⁷Department of Chemistry, Faculty of Mathematics and Science, Universitas Gadjah Mada, Yogyakarta 55281, Indonesia

⁸Information System Study Program, Faculty of Science and Technology, Universitas Airlangga, Jl. Mulyorejo, Surabaya 60115, Indonesia

Received: 28 August 2021/ Accepted: 12 January 2022

Abstract

First-principles calculations are commonly used to search for possible transition states in reaction kinetics studies, which are such a challenge to observe experimentally. However, computationally studying the reaction is also challenging because of, inter alia, the Basis Set Incompleteness Error (BSIE). Accordingly, we utilized density functional theory-based calculations and the complete basis set method, to confirm the conformational effect in the neutral hydrolysis of three ethyl acetate analogs: ethyl formate, ethyl acetate, and ethyl fluoroacetate. The results showed that both methods yielded activation energy span, which implies that the conformational effect in the ethyl acetate neutral hydrolysis is not due to the BSIE. The results also demonstrated the importance of polarization and diffuse function in a basis set. The former was to improve the ground state geometry, and the latter was to increase the activation energy.

Keywords: Complete basis set; conformational effect; density functional theory; energy; neutral hydrolysis

Abstrak

Pengiraan prinsip pertama biasanya digunakan untuk mencari kemungkinan keadaan peralihan dalam kajian kinetik tindak balas, yang merupakan satu cabaran untuk diperhatikan secara uji kaji. Walau bagaimanapun, mengkaji reaksi secara komputasi juga mencabar kerana antara lain Set Asas Ketaklengkapan Ralat (BSIE). Oleh kerana itu, kami melakukan pengiraan berdasarkan teori fungsi ketumpatan dan set asas lengkap, untuk mengesahkan kesan konformasi pada hidrolisis netral tiga analog etil asetat: etil format, etil asetat dan etil fluoroasetat. Hasil kajian menunjukkan bahawa kedua-dua kaedah menghasilkan rentang tenaga pengaktifan, yang menunjukkan bahawa kesan konformasi dalam hidrolisis netral etil asetat bukan disebabkan oleh BSIE. Hasilnya juga menunjukkan pentingnya fungsi polarisasi dan difusi dalam set asas dengan teori fungsi ketumpatan untuk mendapatkan geometri keadaan asas yang lebih tepat dan set asas lengkap untuk meningkatkan tenaga pengaktifan.

Kata kunci: Hidrolisis neutral; kesan konformasi; set asas lengkap; tenaga; teori fungsi ketumpatan

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^*Corresponding author; email: rusydi@fst.unair.ac.id