SAINS MALAYSIANA

Sains Malaysiana 49(6)(2020): 1451-1460

http://dx.doi.org/10.17576/jsm-2020-4906-23

Ab-initio Calculations of the Structural, Electronic and Optical Properties of (CdSe)₂ Clusters

(Penghitungan Ab-initio Sifat Struktur, Elektronik dan Optikal Kelompok (CdSe)₂)

A.I.A. ALSELAWE¹*, MHH JUMALI¹, G. GOPIR¹& M.M. ANAS²

¹School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

²Fakulti Sains dan Teknologi, Universiti Sains Islam Malaysia (USIM), Bandar Baru Nilai, 71800 Nilai, Negeri Sembilan Darul Khusus, Malaysia

Received: 17 December 2019/Accepted: 24 February 2020

ABSTRACT

The distinctive properties of cadmium selenide (CdSe) semiconductor situated it in a multitudinous number of applications. Although (CdSe)₂ cluster has more than one isomer, the previous studies concentrated merely on one isomer. The goal of this study was to determine the various stable geometric structure isomers of (CdSe)₂ clusters; also, structural, electronic, and optical properties of the stable isomers are investigated using density functional theory (DFT). First, geometry optimization calculations of the possible geometric isomers were carried out using the Broyden-Fletcher-Goldfarb-Shanno minimization (BFGS) algorithm. Total ground-state energy calculations showed that all the converged isomers have a high probability of existing in any experiment, relying on the implemented experimental technique. Twenty initial possible geometric structures were investigated, in which eleven isomers were converged. However, all of them are relaxed in the 2D planar geometry. The results showed that eleven possible stable isomers were disclosed, where the final structures of the converged isomers produced six different structures; three of them were not detected before. The rhombus structure was ascertained to be the most stable isomer followed by the trapezoidal structure of (CdSe)₂.The isomers’ Cd-Se bond length are 2.50-2.74 Å, and the average Cd-Se-Cd, Se-Cd-Se angles were 64.5^o-123^o and 56.3^o-114.2^o, respectively. Furthermore, the bond angles show that the selenium atom lone-pairs electrons are responsible for shifting the isomers’ structure from the linearity. The total ground-state energy differences were 0.00-1.82 eV. The calculated highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) gap of the isomers implied that the gap depends on the symmetrical geometry of the isomer. Furthermore, it was evident that the most stable isomers are accompanied with larger gaps. The HOMO-LUMO graphs demonstrated that HOMO orbitals were localized around the selenium atom, while LUMO orbitals were distributed around both cadmium and selenium atoms. The calculated absorption spectrum was unique for each isomer. The absorption edges for the isomers are ranging from 2.53 to 3.73 eV. The results show that the obtained absorption spectra peaks’ values (nm) are smaller compared to CdSe experimental results. (CdSe)₂ clusters are very active that they straightforwardly react to produce larger clusters. Finally, the results of this study corroborate with previous computational studies.

Keywords: Cluster; dimer cadmium selenide; geometry optimization; isomer; rhombus structure

ABSTRAK

Keunggulan sifat semikonduktur kadmium selenida (CdSe) menjadikannya memiliki pelbagai aplikasi dalam bidang elektronik. Meskipun kelompok (CdSe)₂mempunyai lebih daripada satu isomer, namun kajian sebelum ini hanya melaporkan satu isomer sahaja. Tujuan kajian ini dijalankan adalah untuk menentukan kepelbagaian isomer geometri kelompok (CdSe)₂, disamping sifat struktur, elektronik dan pencirian sifat optik ditentukan menggunakan teori fungsian ketumpatan (DFT). Pertama pengiraan pengoptimumam sifat geometri ditentukan menggunakan algoritma Broyden-Fletcher-Geodecker-Shannov(BFGS). Jumlah tenaga keadaan dasar menunjukkan kebarangkalian setiap isomer wujud dalam kajian beruji kaji adalah tinggi, namun bergantung kepada jenis uji kaji yang dijalankan. Sejumlah sebelas daripada dua puluh struktur geometri awal yang dikaji telah berjaya. Manakala semua struktur geometri tersebut menunjukkan keadaan di satah 2D. Keputusan menunjukkan enam daripada sebelas struktur tersebut telah dilaporkan dalam keputusan kajian yang lepas, manakala tiga selebihnya belum dilaporkan sebelum ini. Struktur rombus memberikan keadaan struktur isomer yang paling stabil diikuti dengan struktur trapezoidal (CdSe)₂. Panjang ikatan isomer antara Cd-Se adalah 2.5-2.74 Å dan purata sudut antara Cd-Se-Cd serta Se-Cd-Se adalah 64.5^o-123^o dan 56.3°-114.2°. Tambahan pula, sudut ikatan menunjukkan elektron yang tidak terikat pada atom selenium memainkan peranan mengubah struktur isomer daripada bersifat struktur linear. Jumlah perbezaan jurang nilai tenaga dalam keadaan dasar adalah sekitar 0.00-1.82 eV. Penentuan nilai jarak antara tenaga molekul orbit yang dihuni (HOMO) dan molekul orbit yang tidak dihuni (LUMO) bergantung kepada sifat geometri isomer yang bersimetri. Keputusan kajian menunjukkan isomer yang paling stabil mempunyai nilai jurang tenaga yang lebih besar. Graf taburan elektron menunjukkan orbit HOMO tertumpu di sekitar atom selenium, sementara orbit LUMO terletak di sekitar atom kadmium dan selenium. Spektrum serapan bagi setiap isomer adalah unik antara satu sama lain. Nilai tenaga serapan bermula sekitar 2.53 hingga 3.73 eV. Hasil kajian menunjukkan nilai tenaga pada puncak serapan adalah rendah sedikit berbanding kajian yang dilaporkan dalam kajian CdSe secara uji kaji disebabkan kelompok (CdSe)₂ amat reaktif sehingga membentuk kelompok yang lebih besar. Kesimpulannya, keputusan kajian semasa memberi nilai sokongan kepada keputusan kajian komputasi yang lepas.

Kata kunci: Isomer; kadmium selenida dimer; kelompok; pengoptimum geometri; struktur rombus

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