基于分子转-振光谱精细结构的火焰温度遥测方法

燃烧火焰温度是固体推进剂等重要参数,本文研究了基于分子转-振光谱精细结构的火焰温度遥测方法。根据分子转-振光谱线的展宽机制,研究了分子谱线线型。结合朗伯-比耳吸收定律,去除谱线中心受大气低温气体吸收影响较大的数据点后,利用谱线两翼的数据点进行谱线线型拟合,利用分子转-振光谱精细结构温度遥测方法将经拟合修正后数据反演火焰温度,使得分子转-振光谱精细结构法遥测的火焰温度更为准确。采用加拿大Bomem公司的MR-154傅里叶变换红外光谱仪测量了酒精灯火焰红外发射谱,并根据火焰中水汽的转-振光谱精细结构反演了酒精灯火焰温度为415℃,位于酒精灯火焰温度范围(400—500℃)之内。

Three-Dimensional Ab Initio Potential Energy Surface and Predicted Spectra for the CH_(4)-Ne Complex

We present a new three-dimensional potential energy surface(PES)for CH_(4)-Ne complex.The electronic structure computations were carried out using the coupled-cluster method with singles,doubles,and perturbative triples[CCSD(T)],the augmented correlationconsistent aug-cc-pVXZ(X=T,Q)basis sets were employed with bond functions placed at the mid-point on the intermolecular axis,and the energies obtained were then extrapolated to the complete basis set limit.Analytic intermolecular PES is obtained by least-squares fitting to the Morse/Long-Range(MLR)potential function form.These fits to 664 points have root-mean-square deviations of 0.042 cm^(−1).The bound rovibrational levels are calculated for the first time,and the predicted infrared spectra are in good agreement with the experimental values.The microwave spectra for CH_(4)-Ne dimer have also been predicted for the first time.The analytic PES can be used for modeling the dynamical behavior in CH_(4)-(Ne)N clusters,and it will be useful for future studies of the collision-induced-absorption for the CH_(4)-Ne dimer.

Direct Observation of Electron-Vibration Coupling at MXene-Solvent Interface

MXenes,a new family of two-dimensional(2D)materials,have received extensive interest due to their fascinating physicochemical properties,such as outstandinglight-to-heat conversion efficiency.However,the photothermal conversion mechanism of MXenes is still poorly understood.Here,by using femtosecond visible and mid-infrared transient absorption spectroscopy,the electronic energy dissipation dynamics of MXene(Ti_(3)C_(2)T_(x))nanosheets dispersed in various solvents are carefully studied.Our results indicate that the lifetime of photoexcited MXene is strongly dependent on the surrounding environment.Especially,the interfacial electron-vibration coupling between the MXene nanosheets and the adjacent solvent molecules is directly observed following the ultrafast photoexcitation of MXene.It suggests that the interfacial interactions at the MXene-solvent interface play a critical role in the ultrafast energy transport dynamics of MXene,which offers a potentially feasible route for tailoring the light conversion properties of 2D systems.

四原子分子中Majorana算子矩阵元的新计算公式

李代数方法在研究双原子分子、三原子分子振-转光谱及相关问题等方面已被证明是一种有效方法[1～4], 并被成功推广到多原子分子[5～7]. 构造代数哈密顿量是此方法的关键, 这就要求选择合适的群链. 群链SU(4)SO(4)SO(3)SO(2)已被证明是合适的一条群链[3],并且可以推广到四原子分子[5]. 在代数哈密顿量中, Majorana算子扮演着重要角色. 我们首先研究了3个SO(4)的张量直积得到的耦合张量算子和Majorana算子及其关系, 然后应用广义维格纳-爱卡塔定理, 得到了耦合张量算子矩阵元的一般表达式. 作为特例, 我们计算了四原子分子中Majorana算子的矩阵元, 得到了比文献[4,5]更加简单的计算公式.

High Precision Cavity Ring Down Spectroscopy of 6υ3 Overtone Band of 14N2 16O near 775 nm

Transitions of the 6υ3 overtone band of ^14N2 ^16O near 775 nm have been studied by continuous-wave cavity ring-down spectroscopy. Line positions and intensities were derived from a fit of the line shape using a hard-collisional profile. The line positions determined with absolute accuracy of 5×10^-4 cm^-1 allowed us to reveal finer ro-vibrational couplings taking place after J〉14 except a strong anharmonic interaction identified by the effective Hamiltonian model. The absolute line intensities have also been retrieved with an estimated accuracy of 2% for a majority of the unblended lines. A new set of ro-vibrational and dipole moment parameters were derived from the experimental values. A comparison between the line positions and intensities of the 6υ3 band obtained in this work and those from previous studies is given.

Computer Assisted Assignments of Rotationally Resolved Molecular Spectra

A graphically oriented interactive program for assignments of rotationally resolved molecular spectra has been devised. The program functions by grouping spectral lines in term of the second difference principle. and graphing spectral intensity versus frequency in a bar graph of the selected groups, distinguished by color and/or line-type. This allows for easy detection of regular patterns buried in the observed spectrum. Furthermore, it includes a Loomis-Wood view for assisting in spectral assignments. As an example, the program was applied in assigning the molecular spectrum of the production in the discharge of PCl3 buffered by helium gas, which may belong to several species. The results suggest that the program is highly efficient and quite useful in the assignment and the analysis of molecular spectra, especially those of symmetric top, slightly asymmetric top and linear molecules. The accuracy and efficiency of this program will likely ensure its wide application in the processing of molecular spectra.

Theoretical Studies of Electron Paramagnetic Resonance Parameters for Cr^4＋ Ions in Ca2GeO4 Crystals

The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR parameters for a 3d~2 ion in trigonal MX_4clusters. In these formulas, in addition to the contributions to EPR parameters from the widely usedcrystal-field (CF) mechanism, the contributions from the charge-transfer (CT) mechanism (which areoften neglected) are included. From the calculations, it is found that for the high valence state3d~n ions in crystals, the reasonable explanation of EPR parameters (in particular, the g factors)should take both the CF and CT mechanisms into account.

Electron transfer photochromism of Ln-based(Ln=Dy,Tb)coordinated behavior

Switching on/off single-molecule magnets(SMMs)at room temperature is still a challenge in moleculebased magnets.Herein,two photochromic Ln-based(Ln=Dy,Tb)phosphonate coordinated polymers were synthesized with regulable SMM behavior.The reversible room-temperature photo-coloration was an electron transfer process with a generation of relatively stable radicals,characterized by structural analyses,ultraviolet-visible,luminescence and electron spin resonance spectra and magnetic measurements.Importantly,owing to the antiferromagnetic coupling interactions between Ln^(3+) ions and photogenerated radicals,the room-temperature light irradiation surprisingly switched off the SMM behavior,showing the first example of radicalquenched SMMs in the molecule-based magnets.Moreover,the silient SMM behavior could be recovered after eliminating photogenerated radicals via heat treatment,showing a reversible off/on switch of SMMs via light and heat.This work constructs a system for switching off/on SMMs through electron transfer photochromism,providing a visual operation way via naked-eye-detectable coloration for the switchable SMMs.

Polarized upconversion luminescence from a single LiLuF_(4):Yb^(3+)/Er^(3+) microcrystal for orientation tracking

Polarized upconversion luminescence(UCL)of lanthanide-doped micro/nano-crystals has shown great promise in single-particle tracking and super-resolution bioimaging.However,because of the spectral line broadening and multiple sites of lanthanide in upconversion particles(UCPs),the crystal-field(CF)polarization components of UCL are usually undistinguishable.Herein,we report the linearly polarized UCL in LiLuF_(4):Yb^(3+)/Er^(3+) single microcrystals with resolvable CF transition lines and a polarization degree up to 0.82.The CF levels and CF transition lines of Er^(3+),as well as their emission polarization anisotropy,are unraveled for the first time through low-temperature and high-resolution photoluminescence(PL)and UCL spectroscopies.By taking advantage of the well-resolved and highly-polarized CF transition lines of Er^(3+),we demonstrate the application of LiLuF_(4):Yb^(3+)/Er^(3+) single microcrystals as anisotropic UCL probes for orientation tracking.These findings provide fundamental insights into the polarization anisotropy of UCL in lanthanide-doped single particles,thus laying a foundation for the future design of anisotropic luminescent probes towards versatile applications.