Weilong Liu

Effect of beta-Ring Rotation on the Structures and Vibrational Spectra of beta-Carotene: Density Functional Theory Analysis

The effect of beta-ring rotation on the structures and vibrational spectroscopic characteristics of beta-carotene, including infrared (IR) intensities and Raman activities, is analyzed using density functional theory. Two stable isomers having Ci symmetry are obtained. The reversion of bond lengths is ascribed to the hyperconjugation effect. The natural bond orbital (NBO) charge analysis suggests that the NBO charges of C5 can be used to estimate the degree of pi-electron delocalization. These structural variations are used to analyze and assign the vibrational spectra. It is concluded that (a) the similar rotational angle dependencies of nu1 and nu2 frequencies justify the contribution of C=C stretch vibrations to the nu2 mode and explain the same conjugation length dependencies of nu1 and nu2 frequencies in polyenes, (b) the nu1 mode can be assigned to the C=C stretching in the central part of polyene chain, whereas beta-rings play an important role in nu2 and IR1 bands, especially for the all-trans isomer, and (c) the transition dipole moment of the calculated IR1 absorption band is relevant to the conjugation degree and the crossing angle between the eigenvectors of the polyene chain and the C5=C6 stretching vibration. This theoretical analysis, together with our previous Raman spectral experiments, suggests that the C6-C7 bond is easier to be twisted than other parts of beta-carotene molecule and so provides an insight into the structures of carotenoids and the properties of binding sites in carotenoproteins.

Chemical gases sensing properties of diamond nanocone arrays formed by plasma etching

A uniform diamond nanocone array was formed by plasma etching of diamond film in a hot filament chemical vapor deposition (HFCVD) system. A surface amorphous carbon coating layer, which is formed during CH4/H2 plasma-etching process, was removed by Ar plasma in a reactive ion etching system. The hydrogenation of diamond nanocones was performed in H2 ambience by using the same HFCVD system. The air-diluted NH3 and NO2 gases sensing properties of the diamond cone arrays had been studied by using electric current versus measurement time characteristics at room temperature. The repeatable chemical sensing properties of the hydrogenated diamond cone array sensor are enhanced, in comparison with as-formed diamond film. Surface two-dimensional hole gas structure and greatly increased surface-to-volume ratio both play a key role for the excellent detection performance. As-formed diamond nanocone arrays show a promising prospect for applications as chemical sensor for both reducing (NH3) and oxidizing (NO2) gases.

Red upconversion emission in LiNbO 3 codoped with Er 3+ and Eu 3+

Red upconversion (UC) emission at 626 nm is obtained from a LiNbO(3) crystal codoped with Er(3+) and Eu(3+) under 800 nm femtosecond laser excitation. Energy transfer from ((2)H(11/2,),(4) S(3/2)) levels of Er(3+), which are excited by excited state absorption, to (5)D(1) of Eu(3+) followed by rapidly relaxing to (5)D(0) nonradiatively leads to this red UC emission. The energy transfer efficiency and Er-Eu transfer microparameter of approximately 30% is obtained in LiNbO(3):Er(3+)(1.0 mol%),Eu(3+)(0.1 mol%). These initial experimental results indicate that the red UC emission can be obtained from Er(3+)/Eu(3+) codoped system under diode laser excitation.

Yellow-green upconversion luminescence of Dy3+ ion in LiNbO3 crystal heavily codoped with ZnO

The observed Dy3+ ion upconversion luminescence in LiNbO3 crystal heavily codoped with ZnO was spectrally and temporally analyzed by microsecond time-resolved spectrum under 806nm intense femtosecond laser excitation at room temperature. Absorption spectrum and modified Judd-Ofelt approach were used to investigate its spectroscopic properties. The bright blue and intense yellow emissions are assigned to transitions F9∕24→H15∕26 and F9∕24→H13∕26, respectively. It is concluded that the main upconversion mechanism is excited state absorption by pump power dependence in combination with luminescence intensity temporal evolvements.

Effect of End Groups on the Raman Spectra of Lycopene and β-Carotene under High Pressure

The Raman spectra of all-trans-lycopene in n-hexane were measured under high pressure, and the results compared with those of β-carotene. The different pressure effects on Raman spectra are analyzed taking into account the different structures of lycopene and β-carotene molecules. It is concluded that: (a) the vibronic coupling between the S1 and S0 states of β-carotene is stronger than that of lycopene, (b) the diabatic frequency increment of the ν1 mode is more susceptible to pressure than that of the ν2 mode for lycopene, and (c) β-rings rotation can relieve the pressure effect on the C=C bond length in β-carotene. This work provides some insights for elucidating the structural and environmental effects on Raman spectra of carotenoids.

Enhanced green upconversion emission of Er(3+) through energy transfer by Dy(3+) under 800 nm femtosecond-laser excitation.

Er(3+) green upconversion (UC) emission corresponding to the transition of (4)S(3/2) ((2)H(11/2))-->(4)I(15/2) is enhanced in a Er/Dy-codoped LiNbO(3) crystal compared with Er-doped LiNbO(3) under 800 nm femtosecond-laser excitation at room temperature. The upconversion mechanisms are proposed based on spectral, kinetic, and pump-power dependence analyses. The energy-transfer efficiency from Dy(3+)((4)F(9/2)) to Er(3+)((4)F(7/2)) is 33%, which results in the enhancement of green UC emission. This energy transfer is advantageous for the Er(3+) UC emission sensitized by Dy(3+), especially in a low-phonon-energy host matrix.

Sensitized holmium upconversion emission in LiNbO3 triply doped with Ho3+, Yb3+, and Nd3+

Observed is 15 times enhancement of Ho3+ green upconversion (UC) emission in Ho3+(0.75 mol %)/Nd3+(0.75 mol %) doped lithium niobate crystal after incorporating with 4 mol % of Yb3+ under 800 nm femtosecond laser excitation. Yb3+ acting as bridging ion increases the energy transfer efficiency from Nd3+ F43/2 level to Ho3+ in these triply doped systems. The nonradiative energy transfer efficiency from Nd3+ F43/2 to Yd3+ F25/2 level can reach to 56%. The UC emission mechanisms are proposed based on spectral, kinetic, and pump power dependence analyses. The green UC emission is accomplished through a multi-ion interaction involving ground state absorption by the Nd3+ (I49/2→H29/2,F45/2) followed by three successive energy transfer processes involving one Nd3+-Yb3+ (F43/2+F27/2→I49/2+F25/2) and two Yb3+-Ho3+ pairs (F25/2+I58→F27/2+I56 and F25/2+I56→F27/2+S52,F54); whereas the red is dominated by excited state absorption of the Ho3+ (I57→F55) following two successive energy transfer processes involving the Nd3...

MgO-codoping effects on the spectroscopic properties of Er3+-doped LiNbO3

Optical absorption, spectrally resolved polarized upconversion fluorescence, and time-resolved luminescence spectra are used to investigate the Er3+ spectroscopic properties in a series of congruent LiNbO3 crystals codoped with Er3+ (1 mol %) and MgO (X mol %, X=0, 2, 4, 6, and 8). The absorption spectra indicate that the transition cross section of Er3+ ions decreases with increasing MgO concentration; it is explained as the improvement of the Er3+-site symmetries. A new Er3+ energy site with low energy, which appears in the long wavelength side of the polarized fluorescence spectra for the samples heavily codoped with MgO, is demonstrated in the time-resolved luminescence spectra. An important finding is that mild codoping with MgO clearly does not facilitate the formation of clustered sites, whereas heavy codoping clearly does facilitate it in Er3+-doped LiNbO3 crystals. These results are important to those who consider the material as a 1.5 μm laser or fiber optical cable.

Origin of the Ultrafast Response of the Lateral Photovoltaic Effect in Amorphous MoS2/Si Junctions

The lateral photovoltaic (LPV) effect has attracted much attention for a long time because of its application in position-sensitive detectors (PSD). Here, we report the ultrafast response of the LPV in amorphous MoS2/Si (a-MoS2/Si) junctions prepared by the pulsed laser deposition (PLD) technique. Different orientations of the built-in field and the breakover voltages are observed for a-MoS2 films deposited on p- and n-type Si wafers, resulting in the induction of positive and negative voltages in the a-MoS2/n-Si and a-MoS2/p-Si junctions upon laser illumination, respectively. The dependence of the LPV on the position of the illumination shows very high sensitivity (183 mV mm-1) and good linearity. The optical relaxation time of LPV with a positive voltage was about 5.8 μs in a-MoS2/n-Si junction, whereas the optical relaxation time of LPV with a negative voltage was about 2.1 μs in a-MoS2/p-Si junction. Our results clearly suggested that the inversion layer at the a-MoS2/Si interface made a good contribution to the ultrafast response of the LPV in a-MoS2/Si junctions. The large positional sensitivity and ultrafast relaxation of LPV may promise the a-MoS2/Si junctions applications in fast position-sensitive detectors.

Visible and ultraviolet upconversion emission in LiNbO3 triply doped with Tm3+, Yb3+, and Nd3+

Visible and ultraviolet upconversion (UC) emission is observed under 800 nm femtosecond laser excitation in LiNbO3 crystals triply doped with Tm3+, Yb3+, and Nd3+ at room temperature. Energy transfer (ET) from Nd3+ to Yb3+ then to Tm3+ is very important in this UC emission process. The overlapping between the emissions of D12→F34 and G14→H36, which makes up of blue emission band, is confirmed by transient investigation. From the pump energy dependence investigation, it is known that the dominant populating mechanism for the G14 state is the two-photon process, and that for D12 is the three-photon process. In our UC emission model, the G14 state is populated by the ET of F25/2(Yb3+)+H34(Tm3+)→F27/2(Yb3+)+G14(Tm3+), D12 state is populated by the ET of F32+H34→D12+H36 among Tm3+ ions. For LiNbO3 crystals doped with Tm3+ to the concentration of 0.9 mol %, the measured lifetimes of G14 and D12 are ∼80 and 4 μs.