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

NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC ELECTRON M = Sc – Ni BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN Promoter : Assoc.. Nguyễn Tiến Trung Students : Phan Đặng Cẩm Tú Nguyễn Thanh Thảo Tú Trần Tường

NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC ELECTRON

(M = Sc – Ni) BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN

Promoter : Assoc Prof Dr Nguyễn Tiến Trung Students : Phan Đặng Cẩm Tú

Nguyễn Thanh Thảo Tú Trần Tường Sơn

QUY NHON UNIVERSITY Chemistry Department

A STUDY ON STABILITY, ELECTRONIC STRUCTURE OF DOPED GERMANIUM CLUSTERS

Ge 12 M (M = Sc – Ni) USING COMPUTATIONAL CHEMICAL METHOD

• Introduction

• Theoretical method

• Results and discussion

• Conclusions

• Petitions

OUTLINE

Spectroscope

Optical cable

Medicines IC

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.

1.José M Goicoechea, John E McGrady, Dalton Trans, The Royal Society of Chemistry, 2015, 44, 6755-6766.

2.Debashis Bandyopadhyay, Prasenjit Sen, J Phys Chem., A 2010, 114, 1835-1842.

3.Kapil Dhaka, Debashis Bandyopadhyay, RSC Adv., 2015, 5, 83004–83012.

Ge12Ni: Neha Kapila et al and

Jing Lu: HP.

John E McGrady et al.: BPP.

NGHIÊN CỨU VỀ ĐỘ BỀN VÀ CẤU TRÚC

(M = Sc – Ni) BẰNG PHƯƠNG PHÁP HÓA HỌC TÍNH TOÁN

A STUDY ON STABILITY, ELECTRONIC STRUCTURE OF DOPED GERMANIUM CLUSTERS

Ge 12 M (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 …

Ge12Ti cluster

1 Low-lying isomers of Ge12M (M = Sc-Ni)

RESULTS AND DISCUSSION

Ge12Sc cluster

Sc-1

Doublet [C s; 2A’; 0.00]

Quartet [C1; 4A; 0.20]

Sextet [C s; 6A’; 1.10]

Sc-2

Doublet [C s; 2A’; 0.02]

Quartet [C1; 4A; 0.48]

Sextet [C s; 6A’’; 0.02]

Sc-3

Doublet [C1; 2A; 0.08]

Quartet [C1; 4A; 0.79]

Sextet [C1; 6A; 1.53]

Sc-6

Doublet [C1;2A; 0.70]

Quartet [C1; 4A; 1.30]

Sextet [C1; 6A; 2.14]

Ti-1

Singlet [C1; 1A; 0.00]

Triplet [C 2h; 3Bg; 0.22]

Quintet [C1; 5A; 1.31]

Ti-3

Singlet [C1; 1A; 0.31]

Triplet [C s; 3A’’; 0.63]

Quintet [C s; 5A’’; 1.33]

Ti-4

Singlet [C s; 1A’; 0.47]

Triplet [C1; 3A; 0.94]

Quintet [C1; 5A; 1.75]

Ti-6

Singlet [C1; 1A; 2.19] Triplet [C1; 3A; 2.30] Quintet [C1; 5A; 2.78]

Doublet [C i; 2A; 0.00]

Quartet [D 3d; 4A1g; 0.65]

Sextet [C s; 6A’; 1.64]

V-3

Doublet [C 2v; 2A1; 0.78]

Quartet [C1; 4A; 1.51]

Sextet [C1; 6A; 1.36]

V-4

Quartet [C s; 4A’’; 0.96]

Sextet [C s; 6A; 1.49]

V-5

Quartet [C1; 4A; 1.08] Doublet [C1; 2A; 1.14]

Sextet [C1; 6A; 1.87]

Ge12V cluster

Ge12Cr cluster

Cr-1

Singlet [D 3d; 1A1g; 0.00]

Triplet [C1; 3A; 0.01]

Quintet [C1; 5A; 0.78]

 Cr-3

Singlet [C1; 1A; 0.53]

Triplet [C1; 3A; 0.61]

Quintet [C1; 5A; 0.79]

Cr-4

Triplet [C1; 3A; 0.56]

Quintet [C1; 5A; 0.77]

Singlet [C1; 1A; 1.20]

Cr-5

Triplet [C1; 3A; 2.36] Quintet [C1; 5A; 2.42] Singlet [C1; 1A; 3.16]

Ge12Mn cluster

Ge12Fe cluster

Mn-1

Doublet [D 3d; 2A1g; 0.00]

Quartet [C i; 4Ag; 0.64]

Sextet [C1; 6A; 1.22]

Mn-2

Doublet [C s; 2A”; 0.75]

Quartet [C2; 4A; 0.90]

Sextet [D2; 6B3; 1.64]

Mn-4

Quartet [C1; 4A; 1.29]

Sextet [C i; 6Ag; 0.80]

Mn-5

Doublet [C1;2A; 0.85]

Quartet [C1; 4A; 0.90]

Sextet [C s; 6A’; 1.32]

Fe-1

Triplet [C1; 3A; 0.00]

Singlet [D 3d; 1A1g; 0.20]

Quintet [C1; 5A; 0.47]

Fe-3

Triplet [C1; 3A; 0.38]

Singlet [C1; 1A; 0.40]

Quintet[S4; 5B; 0.75]

Fe-4

Triplet [C1; 3A; 0.87]

Quintet [C1; 5A; 1.71]

Fe-5

Singlet [C1; 1A; 0.45]

Triplet [C1; 3A; 0.56]

Quintet [C1; 5A; 1.03]

Ge12Co cluster

Ge12Ni cluster

Co-1

Doublet [C1; 2A; 0.00]

Quartet [C1; 4A; 0.66]

Sextet [C1; 6A; 1.56]

Co-2

Doublet [C 2h; 2Abg; 0.06]

Quartet [C1; 4A; 0.37]

Sextet [C1; 6A; 1.73]

Co-3

Doublet [C1; 2A; 0.09]

Quartet [C 2v; 4A2; 1.29]

Sextet [C 2v; 6B2; 2.11]

Co-4

Doublet [C s; 2A’’; 0.11]

Quartet [C1; 4A; 0.70]

Sextet [C1; 6A; 1.53]

Ni-1

Singlet [D 2d; 1A1; 0.00]

Triplet [D2; 3B1; 0.53]

Quintet [C1; 5A; 1.15]

Ni-3

Singlet [C s;1A’ ; 0.16]

Triplet [C s; 3A’’ ; 0.54]

Quintet [C1 ; 5A ; 1.38]

Ni-4

Singlet [C1 ;1A ; 0.26]

Triplet [C1; 3A ; 0.30]

Quintet [C 2h; 5Bu; 1.66]

Ni-6

Triplet [C1; 3A ; 0.58]

Quintet [C1 ; 5A ; 1.38]

Ge 12 Sc-1

Doublet [Cs; 2A’; 0.00]

Ge 12 Sc-2

Doublet [C s; 2A’; 0.02]

Ge 12 Sc-3

Doublet [C1; 2A; 0.08]

Ge 12 Ti

Singlet [C1; 1A]

Ge 12 V

Doublet [C i; 2A]

Ge 12 Cr

Singlet [D 3d; 1A1g]

Ge 12 Mn

Doublet [D 3d; 2A1g]

Ge 12 Fe

Triplet [C1; 3A]

Ge 12 Co-1

Doublet [C1;2A; 0.00]

Ge 12 Co-2

Doublet [C 2h; 2Abg; 0.06]

Ge 12 Ni

Singlet [D 2d; 1A1]

There is a change of structures of Ge12M (M = Sc - Ni) series.

 With M = Sc – Fe: the hexagonal prism

(HP).

 With M = Sc – Fe: the hexagonal prism

(HP).

 With M = Co, Ni: the bicapped pentagonal

prism (BPP).

 With M = Co, Ni: the bicapped pentagonal

prism (BPP).

Binding energy of Ge12Ti and Ge12Cr clusters are larger than the

series.

2.1 The Average Binding Energy (BE)

Table 1 Total energy (hartree) of Ge, M, Ge 12 M clusters

and the average binding energy (eV) Ge 12 M 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

2 Stability of clusters

2.2 Embedding Engergy (EE)

Table 2 Embedding enery of Ge 12 M 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

others in series This conclusion consistents with the analysis of the BE above.

2.3 NBO analysis

The maximum of s, d are attained at M = Ti, Cr The bonds between Ti,

It confirms that Ge12Ti and Ge12Cr are more stable than the others in Ge12M series, once more.

M

Electronic

configuration

on M

Electronic configuration on M 

(Ge12M)

s d

Sc 3d1.94s1.9 3d3.764s0.344p1.46 1.56 1.86

Ti 3d2.174s1.83 3d5.344s0.424p1.38 1.41 3.17

V 3d3.84s1.2 3d6.324s0.414p1.34 0.79 2.52

Cr 3d4.044s1.96 3d7.084s0,404p1.24 1.56 3.04

Mn 3d5.994s1.00 3d7.314s0.414p1.17 0.59 1.32

Fe 3d6.984s1.00 3d7.694s0.454p1.18 0.55 0.71

Co 3d7.994s1.00 3d9.114s0.414p1.21 0.59 1.12

Ni 3d10.004s0.00 3d9.604s0.464p1.22 0.46 0.40

(M = Sc – Ni) at different spin states by using computational method

BP86 and Lanl2dz basis set.

lying completely in the cage and the substitution rule is no longer

appropriate.

which, M=Sc-Fe: Hexagonal Prism, M=Co, Ni: Bicapped

Pentagonal Prism.

(M = Sc - Ni) series.

FUTHER WORK

higher level to confirm reliability of the results.

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!