Investigation on Structures and Nonlinear Optical Properties of PPV and Its Derivatives Systems with Adsorbing Alkali Metal Atom†

doi:10.7503/cjcu20150055

Abstract

Abstract:

By means of the density functional theory(DFT) method, we investigated detailedly the structures and nonlinear optical(NLO) properties of the adsorbed phenylenevinylene(PPV) polymer with the alkali metal Li atom and its corresponding derivatives systems decorated with the donor/acceptor group. In these PPV-based systems, the Li atom can be adsorbed stably on the surfaces of PPV and its derivatives, as revealed by their considerable adsorption energies(62.3—78.2 kJ/mol). It is revealed that when adsorbing the Li atom on the [PPV]_n(n=2—4), the evident charge transfer can occur between them, and this effect of lithium salt can effectively enhance the first hyperpolarizabilities β₀ values of PPV systems from original 249—756 a.u. to the range of 1.16×10⁴—1.37×10⁵ a.u. Comparatively, when adsorbing the alkali metal Li atom on the PPV derivatives modified with only donor(—NH₂) or acceptor(—CN) group, the first hyperpolarizabilities of systems can be significantly improved further, where the β₀ values of Li@[NH₂-(PPV)₄] and Li@[(PPV)₄-CN] can be as large as 1.61×10⁵ and 2.85×10⁵ a.u., respectively. This can be attributed to the case that the cooperation effect of lithium salt and Donor-π-Acceptor can result in the more evident decrease of main transition energy of system. Further, this cooperation effect can be strengthened significantly in the Li-adsorbed PPV derivatives decorated with donor/acceptor(—NH₂/—CN) pairs, which can lead to the more effective improvement of β₀ value(up to 3.56×10⁵ a.u. at n=4). This work can provide some new valuable insights for designing the new type of high-performance NLO materials based on the excellent PPV systems.

Key words: Alkali metal Li atom, Phenylenevinylene(PPV), Donor/acceptor group, The first hyperpolarizability, Charge transfer, Nonlinear optical property

CLC Number:

O641

TrendMD:

LI Shaochen, YU Guangtao, CHEN Wei, ZHOU Zhongjun, HUANG Xuri. Investigation on Structures and Nonlinear Optical Properties of PPV and Its Derivatives Systems with Adsorbing Alkali Metal Atom^†[J]. Chem. J. Chinese Universities, 2015, 36(6): 1146.

Figures/Tables 13

Table 1 Static first hyperpolarizability(β0) and the corresponding error*

Method	MP2 6-311++G(3df,3pd)	MP2 6-31+G(d)	M06-2x 6-31+G(d)	B3LYP 6-31+G(d)	HF 6-31+G(d)	CAM-B3LYP 6-31+G(d)	LC-BLYP 6-31+G(d)
β₀/a.u.	11258	11922	11566	11735	12200	13618	13872
Error(%)		5.9	2.7	4.2	8.4	21.0	23.2

Fig.1 Optimized geometries of Li@[PPV]2 [the top(A) and side(B) views] and the general formula of Li@[X-(PPV)n-Y](n=2—4; X, Y=H, —NH2, —CN) systemsThe d value is the vertical distance between the Li atom and benzene ring of [X-(PPV)n-Y].

Fig.2 Optimized geometries of [PPV]n[n=2—4](A1—A3) and Li@[PPV]n(B1—B3)

Table 2 Vertical distance(d) between the Li atom and Li@[PPV]n(n=2—4) systems, the adsorption energies(Ead), NBO charges of doped Li atoms, the polarizability(α), the first hyperpolarizability(β0), the oscillator strength(f0), the transition energy(ΔE), the dipole moment(Δμ) between the crucial excited state and ground state, the estimated values under the two-level approach(Δμ·f0/ΔE3), and the compositions of the crucial transition(CT) state for Li@[PPV]n and [PPV]n

System	d/nm	E_ad/ (kJ·mol^-1)	NBO/e	α/a.u.	β₀/a.u.	f₀	ΔE/eV	Δμ/a.u.	(Δμ·f₀/ ΔE³)/a.u.	CT^*
Li@[(PPV)₂]	0.171	62.3	0.834	310	1.16×10⁴	0.6020	2.907	1.083	534	H→L+9H→L+11
Li@[(PPV)₃]	0.172	66.0	0.837	549	6.29×10⁴	0.7236	2.591	2.054	1720	H→L+1 H→L+5
Li@[(PPV)₄]	0.172	66.9	0.838	783	1.37×10⁵	0.4791	2.360	2.627	1927	H→L+1 H→L+6
[(PPV)₂]				223	249	1.2516	3.835	0.219	98	H→L
[(PPV)₃]				382	518	2.1335	3.351	0.175	200	H-1→L+1 H→L
[(PPV)₄]				555	756	3.0035	3.109	0.147	296	H-1→L+1 H→L

Fig.3 Comparison of the first hyperpolarizability β0 for [PPV]n and Li@[PPV]n systems

Fig.4 Crucial transition states of the Li@[PPV]n(n=2—4) systemsThe relatively large component cofficients are marked.

Fig.5 Optimized geometries of Li@[NH2-(PPV)n](A1—A3), Li@[(PPV)n-NH2](B1—B3), Li@[CN-(PPV)n](C1—C3], Li@[(PPV)n-CN](D1—D3), Li@[NH2-(PPV)n-CN](E1—E3)n=2—4.

Fig.6 Comparison of the first hyperpolarizability β0 values for Li@[PPV]n, Li@[NH2-(PPV)n] and Li@[(PPV)n-NH2] systems(A) and Li@[PPV]n, Li@[CN-(PPV)n] and Li@[(PPV)n-CN] systems(B)

Table 3 Vertical distance(d) between the Li atom and Li@[PPV]n(n=2—4) systems, the adsorption energies(Ead), NBO charges of doped Li atoms, the polarizability(α), the first hyperpolari-zability(β0) for Li@[NH2-(PPV)n], Li@[(PPV)n-NH2], Li@[CN-(PPV)n] and Li@[(PPV)n-CN] systems, respectively

System	d/nm	E_ad/(kJ·mol^-1)	NBO/e	α/a.u.	β₀/a.u.
Li@[NH₂-(PPV)₂]	0.173	67.3	0.846	329	1.18×10⁴
Li@[NH₂-(PPV)₃]	0.173	71.9	0.849	582	7.06×10⁴
Li@[NH₂-(PPV)₄]	0.174	68.6	0.832	831	1.61×10⁵
Li@[(PPV)₂-NH₂]	0.171	54.3	0.831	323	5.69×10³
Li@[(PPV)₃-NH₂]	0.172	62.3	0.835	555	4.16×10⁴
Li@[(PPV)₄-NH₂]	0.172	65.5	0.837	789	1.01×10⁵
Li@[CN-(PPV)₂]	0.171	70.2	0.852	354	2.01×10⁴
Li@[CN-(PPV)₃]	0.171	71.1	0.853	578	5.79×10⁴
Li@[CN-(PPV)₄]	0.171	71.5	0.854	788	9.41×10⁴
Li@[(PPV)₂-CN]	0.173	78.2	0.841	393	2.73×10⁴
Li@[(PPV)₃-CN]	0.172	73.6	0.841	683	1.56×10⁵
Li@[(PPV)₄-CN]	0.172	70.6	0.840	913	2.85×10⁵

Table 4 Oscillator strength(f0), the transition energy(ΔE), the dipole moment(Δμ) between the crucial excited state and ground state, the estimated values under the two-level approach(Δμ·f0/ΔE3), and the compositions of the crucial transition(CT) state for for Li@[NH2-(PPV)n] and Li@[(PPV)n-CN](n=2—4) systems, respectively

System	f₀	ΔE/eV	Δμ/a.u.	(Δμ· f₀/ΔE³)/a.u.	CT
Li@[NH₂-(PPV)₂]	0.7360	2.875	1.907	1189	H→L, H→L+1
Li@[NH₂-(PPV)₃]	0.6424	2.584	2.850	2135	H→L+1, H→L+7
Li@[NH₂-(PPV)₄]	0.5948	2.354	4.245	3895	H→L+2, H→L+3
Li@[(PPV)₂-CN]	0.6532	2.744	1.853	1179	H→L+1, H→L+2
Li@[(PPV)₃-CN]	0.7612	2.363	3.575	4150	H→L, H→L+2
Li@[(PPV)₄-CN]	0.5931	1.444	9.834	38981	H→L, H→L+2

Fig.7 Crucial transition states of the Li@[NH2-(PPV)n], Li@[(PPV)n-CN] and Li@[NH2-(PPV)n-CN] systems(n=2—4) The relatively large component cofficients are marked.

Table 5 Vertical distance(d) between the Li atom and Li@[NH2-(PPV)n-CN](n=2—4) systems, the adsorption energies(Ead), NBO charges of doped Li atoms, the polarizability(α), the first hyperpolarizability(β0), the oscillator strength(f0), the transition energy(ΔE), the dipole moment(Δμ) between the crucial excited state and ground state, the estimated values under the two-level approach(Δμ·f0/ΔE3), and the compositions of the crucial transition(CT) state for Li@[NH2-(PPV)n-CN](n=2—4) systems

System	d/nm	E_ad/ (kJ·mol^-1)	NBO/e	α/ a.u.	β₀/a.u.	f₀	ΔE/ eV	Δμ/ a.u.	(Δμ· f₀/ ΔE³)/a.u.	CT
Li@[NH₂-(PPV)₂-CN]	0.174	84.0	0.853	416	2.74×10⁴	1.0662	2.734	1.860	1953	H→L+1, H→L+9
Li@[NH₂-(PPV)₃-CN]	0.174	75.2	0.836	737	1.80×10⁵	0.5581	1.400	4.553	18635	H→L, H→L+2
Li@[NH₂-(PPV)₄-CN]	0.174	72.7	0.835	987	3.56×10⁵	0.6597	1.363	9.001	47190	H→L, H→L+3

Fig.8 Comparison of the first hyperpolarizability β0 values for Li@[NH2-(PPV)n], Li@[(PPV)n-CN] and Li@[NH2-(PPV)n-CN] systems

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