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Sains Malaysiana 51(7)(2022):
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
KHOIRUNISA1,2, FEBDIAN RUSYDI3,4*, ROICHATUL MADINAH4,5, HERMAWAN
KRESNO DIPOJONO1, FAOZAN AHMAD6, MUDASIR7, IRA
PUSPITASARI4,8 & 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
Diserahkan: 28 Ogos 2021/ Diterima:
12 Januari 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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*Pengarang untuk surat-menyurat; email: rusydi@fst.unair.ac.id
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