Malaysian Journal of
Analytical Sciences Vol 20 No 4 (2016): 946 - 954
DOI:
http://dx.doi.org/10.17576/mjas-2016-2004-30
MOLECULAR
AND ELECTRONIC STRUCTURES OF A NEW RUTHENIUM-TUNGSTEN BIMETALLIC COMPLEX USING DENSITY
FUNCTIONAL THEORY CALCULATIONS
(Struktur
Molekul Dan Elektronik Kompleks Dwilogam Rutenium-Tungsten Berdasarkan
Pengiraan Teori Fungsi Ketumpatan)
Khuzaimah Arifin1*, Wan Ramli Wan Daud1,2, Mohammad B. Kassim1,3
1Fuel Cell Institute
2Department of Chemical
and Process Engineering
3School of Chemical Sciences and Food Technology,
Faculty of Science and Technology
Universiti
Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
*Corresponding author: khuzaim@ukm.edu.my
Received: 5
February 2016; Accepted: 22 April 2016
Abstract
A potential dye sensitizer material for
solar cell composed of a ruthenium-(4, 4’dimethyl-2, 2′-bipyridine)-isothiocyanato-tungsten-[bis-(phenyl-1,
2-ethilenodithiolenic)] bimetallic
complex structure was successfully developed using Density Functional Theory
(DFT) calculations. The optimal structure
was realized by calculations using the generalized gradient approximation (GGA) framework in a
double numeric plus polarization (DNP) basis set using
the following three functional
methods: Becke-Pardew
(BP), Becke-Lee-Yang-Parr (BLYP)
and Perdew-Burke-Ernzerhof (PBE). The PBE
calculation gave a structure with
bond lengths and angles that approximated
the experimental data. The restricted-spin calculation of PBE
found that BM has
339 molecular orbitals in which the
highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)
are located at orbital numbers 312
and 313, respectively.
The HOMO was delocalized over the W(S2C2) ring, the
ruthenium metal center
and the thiocyanate bridging ligand. In contrast, the LUMO
was found mainly at the bipyridyl
ligand with a small contribution from
the ruthenium metal center.
Electron excitation from the HOMO ® LUMO occurred at 2964 nm
with an excitation energy of 0.42 eV, which is depicted by the charge transfer from one metal to
another (intervalence charge transfer, IVCT) or as a manifestation
of the NCS bridging ligand.
Keywords: density functional theory, bimetallic,
thiocyanate, bridging ligand
Abstrak
Pembangunan struktur molekul kompleks dwilogam
rutenium-(4,4’dimetil-2,2′-bipiridina)-isotiosianat-tungsten[bis-(fenil-1,2-etilenoditiolena)]
(BM) telah dilakukan menggunakan kaedah pengkomputeran Teori Fungsi Ketumpatan (DFT) berdasarkan data
yang diperoleh dari eksperimen. Untuk mendapatkan struktur yang optimum, pengiraan telah dilakukan dengan menggunakan
pendekatan gradien menyeluruh (GGA)
dengan set asas pengutuban tambahan gandaan angka (DNP)
pada tiga kaedah fungsian; Becke-Pardew (BP), Becke-Lee-Yang-Parr
(BLYP) dan Perdew–Burke–Ernzerhof (PBE). Pengiraan
menggunakan fungsian PBE menghasilkan struktur dengan panjang dan sudut ikatan
yang paling mendekati nilai eksperimen. Hasil pengiraan spin terhad dengan PBE
mendapati bahawa kompleks BM memiliki 339 orbital molekul, di mana orbital
molekul berisi tertinggi (HOMO) dan orbital molekul tak berisi terendah (LUMO)
masing-masing berada pada orbital molekul 312 dan 313. Orbital HOMO kompleks
dwilogam BM didapati dinyah setempat pada gelang W(S2C2),
logam pusat Ru serta ligan penghubung NCS. Sebaliknya, orbital LUMO sebahagian
besarnya berada pada ligan bipiridil dengan sedikit sumbangan dari logam pusat
Ru. Tenaga pengujaan elektron dari HOMO ® LUMO wujud sebagai puncak penyerapan pada 2964 nm dengan
tenaga pengujaan 0.42 eV yang berpadanan dengan peralihan cas daripada logam
kepada logam (peralihan cas antara velensi, IVCT) yang menyokong peranan NCS
sebagai ligan titian.
Kata kunci: teori fungsi ketumpatan, kompleks
dwilogam, thiosianat, ligan penghubung
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