Slide Hóa học: NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC ELECTRON CỦA DÃY CLUSTER Ge12M (M = Sc – Ni) BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN

QUY NHON UNIVERSITY Chemistry Department NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC ELECTRON CỦA DÃY CLUSTER Ge 12M (M = Sc – Ni) BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN A STUDY ON STABILITY, ELECTRONIC STRUCTURE OF DOPED GERMANIUM CLUSTERS Ge12M (M = Sc – Ni) USING COMPUTATIONAL CHEMICAL METHOD Promoter : Assoc Prof Dr Nguyễn Tiến Trung Students : Phan Đặng Cẩm Tú Nguyễn Thanh Thảo Tú Trần Tường Sơn OUTLINE • Introduction • Theoretical method • Results and discussion • Conclusions • Petitions INTRODUCTION Optical cable Spectroscope IC Medicines Ge12M clusters Ge12Cr: Neha Kapila et al.: Ge13 structure with C2v symmetry with one Ge atom replaced by Cr John E McGrady: the perfect icosahedra Kapil Dhaka and D Bandyopadhyay: HP Ge12Ni: Neha Kapila et al and Jing Lu: HP John E McGrady et al.: BPP 1.José M Goicoechea, John E McGrady, Dalton 2.Debashis Bandyopadhyay, Prasenjit Sen, 3.Kapil Dhaka, Debashis Bandyopadhyay, RSC Adv., 2015, 5, 83004–83012 Trans, J The Phys Royal Society Chem., of A Chemistry, 2010, 2015, 44, 114, 6755-6766 1835-1842 NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC ELECTRON CỦA DÃY CLUSTER Ge 12M (M = Sc – Ni) BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN A STUDY ON STABILITY, ELECTRONIC STRUCTURE OF DOPED GERMANIUM CLUSTERS Ge12M (M = Sc – Ni) USING COMPUTATIONAL CHEMICAL METHOD THEORETICAL METHOD • • Computational method BP86; the Lanl2dz basis set Some other softwares: Gaussian 03, GaussView 05, Corel Draw, Origin, JMol, NBO 5.G … RESULTS AND DISCUSSION Low-lying isomers of Ge Ge 12 12 M (M = Sc-Ni) Sc cluster Sc-1 Sc-2 Sc-3 Doublet [Cs; A’; 0.00] Doublet [Cs; A’; 0.02] Doublet [C1; A; 0.08] Quartet [C1; A; 0.20] Quartet [C1; A; 0.48] Quartet [C1; A; 0.79] Sextet [Cs; A’; 1.10] Sextet [Cs; A’’; 0.02] Sextet [C1; A; 1.53] Ge 12 Sc-6 Doublet [C1; A; 0.70] Quartet [C1; A; 1.30] Sextet [C1; A; 2.14] Ti cluster Ti-1 Ti-3 Ti-4 Ti-6 Singlet [C1; A; 0.00] Singlet [C1; A; 0.31] Singlet [Cs; A’; 0.47] Singlet [C1; A; 2.19] Triplet [C2h; Bg; 0.22] Triplet [Cs; A’’; 0.63] Triplet [C1; A; 0.94] Triplet [C1; A; 2.30] Quintet [C ; A; 1.31] Quintet [C ; A’’; 1.33] Quintet [C ; A; 1.75] Quintet [C ; A; 2.78] Ge 12 V cluster V-1 V-3 V-4 V-5 Doublet [Ci; A; 0.00] Doublet [C2v; A1; 0.78] Quartet [Cs; A’’; 0.96] Quartet [C1; A; 1.08] Quartet [D3d; A1g; 0.65] Quartet [C1; A; 1.51] Sextet [Cs; A; 1.49] Doublet [C 1; A; 1.14] Sextet [Cs; A’; 1.64] Sextet [C1; A; 1.36] Sextet [C1; A; 1.87] Ge Cr cluster 12     Cr-1 Singlet [D3d; A1g; 0.00] Triplet [C1; A; 0.01] Cr-3 Singlet [C1; A; 0.53] Triplet [C1; A; 0.61] Quintet [C ; A; 0.79] Cr-4 Cr-5 Triplet [C1; A; 0.56] Triplet [C 1; A; 2.36] Quintet [C1; A; 0.77] Quintet [C 1; A; 2.42] 1 Ge12Mn cluster Mn-1 Mn-5 Mn-2 Mn-4 Doublet [D3d; A1g; 0.00] Doublet [Cs; A”; 0.75] Quartet [Ci; Ag; 0.64] Quartet [C2; A; 0.90] Sextet [C1; A; 1.22] Sextet [D2; B3; 1.64] Quartet [C1; A; 1.29] Sextet [Ci; Ag; 0.80] Doublet [C1; A; 0.85] Quartet [C1; A; 0.90] Sextet [Cs; A’; 1.32] Ge Fe cluster 12 Fe-1 Fe-3 Triplet [C1; A; 0.00] Triplet [C1; A; 0.38] Singlet [D3d; A1g; 0.20] Singlet [C1; A; 0.40] Quintet [C1; A; 0.47] Quintet[S4; B; 0.75] Fe-4 Triplet [C1; A; 0.87] Quintet [C1; A; 1.71] Fe-5 Singlet [C1; A; 0.45] Triplet [C1; A; 0.56] Quintet [C1; A; 1.03] Ge 12 Co cluster Co-1 Co-2 Co-3 Co-4 Doublet [C1; A; 0.00] Doublet [C2h; Abg; 0.06] Doublet [C1; A; 0.09] Doublet [Cs; A’’; 0.11] Quartet [C1; A; 0.66] Quartet [C1; A; 0.37] Quartet [C2v; A2; 1.29] Quartet [C1; A; 0.70] Sextet [C1; A; 1.56] Sextet [C1; A; 1.73] Sextet [C2v; B2; 2.11] Sextet [C1; A; 1.53] Ge12Ni cluster Ni-1 Ni-3 Ni-4 Singlet [D2d; A1; 0.00] Singlet [Cs; A’ ; 0.16] Singlet [C1 ; A ; 0.26] Triplet [D2; B1; 0.53] Triplet [Cs; A’’ ; 0.54] Triplet [C1; A ; 0.30] Quintet [C1; A; 1.15] Quintet [C1 ; A ; 1.38] Quintet [C2h; Bu; 1.66] Ni-6 Triplet [C1; A ; 0.58] Quintet [C1 ; A ; 1.38] There is a change of structures Ge12Sc-1 Ge12Sc-2 Ge12Sc-3 Doublet [Cs; A’; 0.00] Doublet [Cs; A’; 0.02] Doublet [C1; A; 0.08] of Ge12M (M = Sc - Ni) series  With M = Sc – Fe: the hexagonal Ge12Ti Ge12V Ge12Cr Singlet [C1; A] Doublet [Ci; A] Singlet [D3d; A1g] prism (HP)  Ge12Mn Ge12Fe Doublet [D3d; A1g] Triplet [C1; A] Ge12Co-1 Ge12Co-2 Ge12Ni Doublet [C1; A; 0.00] Doublet [C2h; Abg; 0.06] Singlet [D2d; A1] With M = Co, Ni: pentagonal prism (BPP) the bicapped Stability of clusters 2.1 The Average Binding Energy (BE) Table Total energy (hartree) of Ge, M, Ge 12M clusters and the average binding energy (eV) Ge12M clusters M E(M) E(Ge12M) BE(Ge12M) Sc -46.383887 -92.234244 2.93 Ti -57.563391 -103.903463 3.96 V -71.2276617 -117.169488 3.13 Cr -86.0482997 -132.146831 3.46 Mn -103.797821 -149.795072 3.25 Fe -123.293246 -169.328687 3.33 Co -145.074091 -190.979333 3.05 Ni -169.165082 -215.228832 3.39 Binding energy of Ge12Ti and Ge12Cr clusters are larger than the others, so Ge 12Ti and Ge12Cr are more stable than the others in series 2.2 Embedding Engergy (EE) Table Embedding enery of Ge 12M clusters (M = Sc – Ni) M E(M) E(Ge12M) EE(Ge12M) Sc -46.383887 -92.24453497 6.53 Ti -57.563391 -103.9145169 19.14 V -71.2276617 -117.1807734 8.10 Cr -86.0482997 -132.1589141 12.94 Mn -103.797821 -149.8071398 10.12 Fe -123.293246 -169.340142 10.31 Co -145.074091 -190.9903935 7.53 Ni -169.165082 -215.2398543 11.64 Removing Ti, Cr atoms from Ge12Ti, Ge12Cr required more energy than the others in series This conclusion consistents with the analysis of the BE above 2.3 NBO analysis Electronic configuration Electronic configuration on M on M (Ge12M) ∆s ∆d 3.76 0.34 1.46 4s 4p 1.56 1.86 5.34 0.42 1.38 4s 4p 1.41 3.17 6.32 0.41 1.34 3d 4s 4p 0.79 2.52 M Sc Ti V 3d 1.9 1.9 4s 2.17 1.83 3d 4s 3d 3.8 1.2 4s 3d 3d Cr 4.04 1.96 3d 4s 3d 7.08 0,40 1.24 4s 4p 1.56 3.04 Mn 5.99 1.00 3d 4s 7.31 0.41 1.17 3d 4s 4p 0.59 1.32 Fe 6.98 1.00 3d 4s 3d 7.69 0.45 1.18 4s 4p 0.55 0.71 Co 7.99 1.00 3d 4s 9.11 0.41 1.21 3d 4s 4p 0.59 1.12 Ni 10.00 0.00 3d 4s 3d 9.60 0.46 1.22 4s 4p 0.46 0.40 The maximum of ∆s, ∆d are attained at M = Ti, Cr The bonds between Ti, Cr and Ge atoms in Ge 12Ti and Ge12Cr are stronger than other clusters It confirms that Ge12Ti and Ge12Cr are more stable than the others in Ge12M series, once more CONCLUSIONS • Has found more than 100 stable isomers of Ge12M clusters (M = Sc – Ni) at different spin states by using computational method BP86 and Lanl2dz basis set • Identified the lowest-lying isomers of Ge12M clusters (M = Sc – Ni) The ground states of Ge 12M favor cage structures with dopant atoms lying completely in the cage and the substitution rule is no longer appropriate • There is a change of structures of Ge12 M (M = Sc - Ni) series In which, M=Sc-Fe: Hexagonal Prism, M=Co, Ni: Bicapped Pentagonal Prism • Results of BE, EE, VEA and NBO analysis show that Ge12Ti and Ge12Cr clusters are more stable than the others in Ge12M (M = Sc - Ni) series FUTHER WORK • Continue to optimize stable structures of Ge 12M clusters at higher level to confirm reliability of the results • Expand the study on structure and stability of Ge 12M clusters at different charge states, such as: cation or anion, to find out low-lying isomers with high symmetry • Do further research on electron distribution and dependence of stability on geometrical and electronic structures to find out the rule which has an affect on the stabilities of these clusters Thanks for your attention! ... ELECTRON CỦA DÃY CLUSTER Ge 12M (M = Sc – Ni) BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN A STUDY ON STABILITY, ELECTRONIC STRUCTURE OF DOPED GERMANIUM CLUSTERS Ge12M (M = Sc – Ni) USING COMPUTATIONAL CHEMICAL... Bandyopadhyay, RSC Adv., 2015, 5, 8300 4–8 3012 Trans, J The Phys Royal Society Chem., of A Chemistry, 2010, 2015, 44, 114, 6755-6766 1835-1842 NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC ELECTRON CỦA DÃY CLUSTER. .. isomers of Ge12M clusters (M = Sc – Ni) at different spin states by using computational method BP86 and Lanl2dz basis set • Identified the lowest-lying isomers of Ge12M clusters (M = Sc – Ni) The