硼掺杂增强g-C3N4基单原子催化剂性能的第一性原理研究

单原子催化剂(SACs)以其最大的金属原子利用率和较高的催化活性而备受关注.本文提出了在Mn负载g-C₃N₄单层(Mn/g-C₃N₄)中进行B掺杂的方案来提升单原子催化剂的光催化活性,并利用第一性原理对Mn/B-g-C₃N₄单原子催化剂的晶体结构,电子结构,带边位置和光学性质进行计算.计算结果表明B掺杂具有较强的结构稳定性,带隙变小,同时带隙中出现杂质能级,导致吸收边向可见光区发生红移,提高了g-C₃N₄在太阳光下光吸收能力和光催化活性,研究结果为制备高效的g-C₃N₄基光催化SACs提供了理论指导.     

一类金属卤化物中孤对电子立体化学活性 及其对双折射率的影响机制研究

双折射材料广泛应用在激光通讯等工程和研究领域。本文使用第一性原理方法研究了后过渡金属卤化物PbX2和BiX3(X=Cl, Br, I)的电子结构与双折射率。计算结果表明,PbX2和BiX3(X=Cl,Br,I)中阳离子孤对电子立体化学程度自X=Cl至X=I逐渐减弱。原子轨道计算分析表明M s-X p (M为阳离子,X为卤素)轨道能级差值决定阳离子孤对电子立体化学活性程度;能级差值越大,孤对电子立体化学活性程度越弱。费米面附M p轨道极大影响材料双折射率的大小,因而使得这些材料的双折射率从X=Cl至X=I逐渐增强。     

HL-2A装置第一壁石墨组件研究

HL-2A装置的第一壁由石墨构件、Cu偏滤器靶板和AISI 304LN不锈钢真空室内壁组成。石墨构件总重量为44kg,覆盏面积为2．80,覆盖率为2．2％。由于HL-2A装置所用石墨件材料均为历经长期托卡马克实验和长期暴露大气的石墨材料,因此石墨构件的处理效果显得更为重要。介绍了EK98、SMF-800石墨材料、ASDEX装置用CFC、国产CFC的研究结果和HL-2A装置第一壁石墨材料预处理及其结果。     

非晶碳薄膜振动拉曼光谱的第一性原理研究

采用基于第一性原理的赝势平面波方法,对3个不同密度(2.6,2.9和3.2 g·cm-3)非晶碳结构的振动态密度和振动拉曼光谱进行了研究。结构模型由快速“液体-淬火”方法模拟得到,振动频率和本征模由线性响应理论决定,拉曼耦合张量由有限电场方法计算。计算结果表明：当密度从2.6增加到3.2 g·cm-3时,sp3碳含量从50%增加到84.4%,G峰向高频区偏移,D峰和G峰的强度之比I_D/I_G减小,T峰向低频区偏移且T峰和G峰的强度之比I_T/I_G增大。该结果与实验结果显示出很好的一致性。依据原子振动的分析结果证实：拉曼光谱的G峰和D峰均来自于sp2碳原子的振动贡献,且G峰是由任何成对的sp2碳原子的伸缩振动产生的,T峰来自于sp3杂化碳原子的振动贡献,G峰和T峰峰位随结构的色散是由键长变化导致的。     

第一性原理研究LuAlO3中掺杂Ce3+的4f-5d跃迁性质

We have investigated properties of the compound LuAlO₃:Ce³⁺ associated with the Ce³⁺ 4f-5d transition by using the periodic density functional theory. A hybrid functional has been used for the 4f states and a constrained approach has been employed for the excited 5d state. It is found that the average distance between Ce³⁺ and the eight nearest-neighbor O atoms decrease by 0.05 ?on going from 4f to 5d state. The calculated Stokes shift is in good agreement with experiment. Based on the optimized structure around Ce³⁺, the energy level scheme of the 5d states has been evaluated using the angular overlap model, in reasonable agreement with experiment.     

First eigenvalue of birth-death processes with killing

In this paper, we present an explicit and computable lower bound for the first eigenvalue of birth-death processes with killing. This estimate is qualitatively sharp for birth-death processes without killing. We also establish an approximation procedure for the first eigenvalue of the birth-death process with killing by an increasing principal eigenvalue sequence of some birth-death processes without killing. Some applications of our results are illustrated by many examples.     

Enhanced gas sensing performance of polyaniline incorporated with graphene: A first-principles study

Conducting polymers such as polyaniline (PANI) are potential sensing materials for ammonia due to their fast response and low cost, however, the corresponding sensing mechanism needs to be studied further. In this paper, molecular dynamic and first-principles simulations are carried out to investigate ammonia sensing mechanisms of polyaniline/graphene heterostructure. The adsorption of ammonia at different locations of pure polyaniline and graphene/PANI composites is analyzed. The band gap for graphene/PANI system shows more significant change after adsorption than that of pure polyaniline, which indicates higher sensitivity for detecting ammonia, and the results of sorption isotherm imply that graphene/PANI system exhibits more adsorption capacity for ammonia. Moreover, diffusion coefficient of ammonia in polyaniline/graphene system is much large than that of pure polyaniline, demonstrating that gas diffusion occurs more easily in the heterostructure. The results are verified by experimental data, and the proposed computational frame can be used to evaluate and design nanocomposite materials for gas sensor.     

Explosive synchronization through dynamical environment

We report the emergence of an explosive synchronization transition in the identical oscillators interacting indirectly through a network of dynamical agents. The transition from incoherent state to coherent state and vice–versa in these coupled oscillator exhibits an abrupt as well as irreversible. Such transition depends on the network topology as well as the interaction between the oscillators and dynamical agents rather than degree-frequency correlation in the network of oscillators. The occurrence of explosive synchronization is studied in details by using an appropriate order parameter for limit-cycle oscillators with respect to the different parameters like rewiring probability, average degree, and diffusion rate in dynamical agents.     

NO在Ni_xAg_y(x+y=13)团簇表面吸附分解的第一性原理研究

基于第一性原理计算方法,对Ni_xAg_y(x+y=13)团簇的几何结构进行优化后,研究了NO在此类团簇表面不同位置的吸附分解行为,讨论了团簇的束缚能、束缚能的二阶差分、能隙以及吸附前后键长、吸附能、NO分波态密度的变化情况.结果表明,团簇对称性随着Ni的占比变化而变化,稳定性随Ni占比增加而增强,束缚能的二阶差分随着Ni原子的增多呈现奇偶震荡性,NO@Ni_xAg_y(x+y=13)团簇表面吸附行为主要为化学吸附,吸附后N-O键长的变化在0.028?～0.092?之间.对团簇吸附NO的态密度分析发现,吸附后NO的2π*轨道失去电子,1π轨道得到电子,从而导致吸附能的变化.