(Mg(BH_4)_2)_n团簇结构与性质的密度泛函理论研究

采用了密度泛函理论中的杂化密度泛函B3LYP方法,在6-31G*基组水平上对[Mg(BH_4)_2]_n(n=1-3)团簇的结构进行了优化,几何结构优化时自旋多重度取了1、3、5等多种情况进行计算.最后对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了研究.结论表明:团簇最稳定结构易形成链状结构,其中Mg-B键长为0.210～0.253 nm,-BH_4基中靠近Mg原子处的B-H键长约为0.125 nm、远离Mg原子处的B-H键长为0.119 nm.对比团簇和晶体的光谱结构表明,-BH_4基在团簇和晶体中结构基本一致.Mg原子的自然电荷在1.687～1.757e之间,B原子的自然电荷在-0.702～-0.788e之间,H原子基本不参与电荷转移,其自然电荷在-0.094～0.070e之间.团簇中Mg原子和-BH_4基之间相互作用呈现较强的离子性,Mg(BH_4)_2团簇具有相对较高的动力学稳定性.     

(Mg(BH_4)_2)_n团簇结构与性质的密度泛函理论研究

采用了密度泛函理论中的杂化密度泛函B3LYP方法,在6-31G*基组水平上对[Mg(BH_4)_2]_n(n=1-3)团簇的结构进行了优化,几何结构优化时自旋多重度取了1、3、5等多种情况进行计算.最后对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了研究.结论表明:团簇最稳定结构易形成链状结构,其中Mg-B键长为0.210～0.253 nm,-BH_4基中靠近Mg原子处的B-H键长约为0.125 nm、远离Mg原子处的B-H键长为0.119 nm.对比团簇和晶体的光谱结构表明,-BH_4基在团簇和晶体中结构基本一致.Mg原子的自然电荷在1.687～1.757e之间,B原子的自然电荷在-0.702～-0.788e之间,H原子基本不参与电荷转移,其自然电荷在-0.094～0.070e之间.团簇中Mg原子和-BH_4基之间相互作用呈现较强的离子性,Mg(BH_4)_2团簇具有相对较高的动力学稳定性.     

[Mg(NH2)2]n(n=1—5)团簇的密度泛函理论研究

用密度泛函理论的杂化密度泛函B3LYP方法在6-31G*基组水平上对[MS(NH2)2]n(n=1-5)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究.结果表明:团簇易形成链状结构,Mg-N键长为0.190-0.234 nm,N-H键长为0.101-0.103 nm,H-N-H键角为100.2°-107.5°;团簇中Mg原子的自然电荷在1.585e-1.615e之间,N原子的自然电荷在-1.551 e--1.651 e之间,H原子的自然电荷在0.369e-0.403e之间,-NH2基的自然电荷在-0.784e--0.845e之间,Mg原子和-NH2基之间相互作用呈现较强的离子性.团簇结构及光谱与晶体比较表明,-NH2基在团簇和晶体中均保持其完整性.     

(MgB2)n(n=1～3)团簇结构与性质的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3IJYP方法在6-31G*基组水平上对(MgB2)n(n=1～3)团簇各种可能的构型进行几何结构优化,预测各团簇的最稳定结构,并对其振动特性、成键特性、极化率和超极化率等性质进行理论研究.结果表明,团簇的几何结构大多是平面结构,团簇的稳定结构中通常是几个呈负电性的B原子形成一个负电中心,而其他B原子和Mg原子处在端位,且显正电性,Mg原子的自然电荷在 0.559e～ 0.920e之间,B原子的自然电荷在-0.724e～ 0.197e之间;团簇中通常是B-B键和B-Mg键共存,较少出现Mg-Mg键,计算得到的B-B键键长在0.153～0.182 nm之间,B-Mg键键长在0.218～0.231 nm之间.     

(LiN3)n(n=1～2)团簇的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(LiN3)n(n=1～2)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性和电荷布局等性质进行了理论研究.结果表明,LiN3团簇最稳定构型为直线构型;(LiN3)n(n=1～2)团簇中N-N键长在0.1146～0.1203 nm之间,N-Li键长在0.1722～0.1987 nm之间;Li原子的自然电荷在0.708 e～0.907 e之间,N原子的自然电荷在-0.896 e～0.208 e之间.     

(Li3N)n(n=1-5)团簇结构与性质的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(Li3N)n(n=1-5)团簇各种可能的构型进行儿何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究.结果表明,(Li3N)n(n=1-5)团簇中N原子的配位数以4,5较多见,"Li-Li键长为0.210-0.259 nm,Li原子在桥位时Li-N键长为0.185-0.204 nm,Li原子在端化时Li-N键长为0.172-0.178nm;团簇中N原子的平均自然电荷为-2.01 e,Li原子的平均自然电荷为 0.67e;Li3N,(Li3N)5团簇有相对较高的动力学稳定性.     

(Ca3N2)n(n=1-4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(Ca3N2)n(n=1-4)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了理论分析.结果表明,(Ca3N2)n(n=1-4)团簇最稳定构型中N原子为3-5配位,Ca-N键长为0.231-0.251 mm,Ca-Ca键长为0.295-0.358 nm;N原子的自然电荷在-1.553 e--2.241 e之间,Ca原子的自然电荷在1.035e-1.445e之间,Ca和N原子间相互作用呈现较强的离子性,Ca3N2和(Ca3N2)3团簇有相对较高的动力学稳定性.     

(LiN3)n(n=1～2)团簇结构与性质的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(LiN3)n(n=1～2)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性和电荷布局等性质进行了理论研究.结果表明,LiN3团簇最稳定构型为直线构型;(LiN3)n(n=1～2)团簇中N-N键长在0.1146～0.1203nm之间,N-Li键长在0.1722～0.1987nm之间;团簇中Li原子全部显正电性,越靠近Li原子的N原子负电性越强,在直线构型的N3-离子中,两端的N原子均具负电荷,而中心N原子具正电荷.     

(Ca3N2)n(n=1—4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G^*基组水平上对(Ca₃N₂)_n(n=1—4)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了理论分析.结果表明,(Ca₃N₂)_n(n=1—4)团簇最稳定构型中N原子为3—5配位,Ca—N键长为0.231—0.251nm,Ca—Ca键长为0.295—0.358nm;N原子的自然电荷在-1.553e—-2.241e之间,Ca原子的自然电荷在1.035e—1.445e之间,Ca和N原子间相互作用呈现较强的离子性,Ca₃N₂和(Ca₃N₂)₃团簇有相对较高的动力学稳定性. 关键词： 3N₂)_n(n=1—4)团簇')" href="#">(Ca₃N₂)_n(n=1—4)团簇 密度泛函理论 结构与性质     

(Li3N)n(n=1—5)团簇结构与性质的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(Li₃N)_n(n=1—5)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构. 并对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究. 结果表明,(Li₃N)_n(n=1—5)团簇中N原子的配位数以4,5较多见,Li—Li键长为0.210—0.259nm,Li原子在桥位时Li—N键长为0.185—0.204nm,Li原子在端位时Li—N键长为0.172—0.178nm;团簇中N原子的平均自然电荷为-2.01e,Li原子的平均自然电荷为+0.67e;Li₃N,(Li₃N)₅团簇有相对较高的动力学稳定性. 关键词： 3N)_n(n=1—5)团簇')" href="#">(Li₃N)_n(n=1—5)团簇 密度泛函理论 结构与性质 储氢材料     

关于光子角动量问题的来信

关于光子角动量问题的来信编辑同志：看了１９９８年第１期《大学物理》刊登的读者来信，想说几点看法：１）沿动量方向的自旋分量并不是沿固定方向的自旋分量．在经典物理中，因为粒子有确定的动量，所以，沿其方向的自旋分量当然也是一种沿固定方向（该动量方向）的自旋...     

Theoretical Study of the Collision-Induced Double Transition CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) at 296 K

A procedure is presented for the calculation of the double vibrational collision-induced absorption CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) on the basis of quantum lineshapes computed using an isotropic potential and dipole-induced dipole functions. The linestrengths and energies of the vibration-rotation transitions are treated explicitly for N(2), utilizing the HITRAN database for CO(2). The theoretical absorption profile is compared to recent experimental results. By narrowing the width of the individual lines contributing to the overall absorption profile relative to their values determined for N(2)-N(2) collision-induced absorption, excellent agreement between theory and experiment is obtained. Copyright 2000 Academic Press.     

First Observation of the nu(17)-nu(4) Difference Bands of Diborane (10)B(2)H(6) and (11)B(2)H(6)

An analysis of the nu(17)-nu(4) difference bands near 800 cm(-1) of two isotopic species, (10)B(2)H(6) and (11)B(2)H(6), of diborane has been carried out using infrared spectra recorded with a resolution of ca. 0.003 cm(-1). In addition, the nu(17) band of (10)B(2)H(6) has been recorded and assigned. Since this band in (11)B(2)H(6) had already been studied (R. L. Sams, T. A. Blake, S. W. Sharpe, J.-M. Flaud, and W. J. Lafferty, J. Mol. Spectrosc. 191, 331-342 (1998)), it was possible to derive precise energy levels and Hamiltonian constants for the 4(1) vibrational states of both isotopic species. Copyright 2000 Academic Press.     

The 2(3)Delta(g) State of (7)Li(2)

Using pulsed perturbation-facilitated optical-optical double resonance (PFOODR) spectroscopy, the 2(3)Delta(g) state of (7)Li(2) (electronic configuration (varsigma(g)2s) (4ddelta(g)), effective principal quantum number n* = 4.101) has been observed and assigned. Molecular constants and a RKR potential energy curve were obtained. The major molecular constants are Copyright 2000 Academic Press.     

CO2同位素分子16O12C16O, 16O12C17O, 16O13C17O配分函数研究

本文主要研究了CO2的三种同位素分子16O12C16O , 16O12C17O ,16O13C17O 70 K~6000 K的总内配分函数 (TIPS)。在总内配分函数的计算中, 转动配分函数的计算采用了McDowell的解析式法, 振动配分函数则采用了简谐振动近似(HOA)获得。最后通过将两配分函数乘积近似计算得出TIPS, 并将其70~3000 K的数据和HITRAN04数据进行了比较, 发现所得结果和数据库符合的较好, 且其误差可以近似看成一条直线。并通过对误差的拟合修订了高温区(3000~6000 K)的计算数据, 给出了在高温下的较为准确的TIPS值。     

The Perturbation between the G(1)Pi(g) and 2(1)Delta(g) States of (7)Li(2)

We have observed the rotational levels in the v = 2, 3, 5, 6, 7, and 8 vibrational manifolds of the 2(1)Delta(g) state of (7)Li(2) via the A(1)Sigma(+)(u) intermediate levels by DeltaLambda = 2 transitions. This violation of the DeltaLambda = 0, +/-1 selection rule is due to the interaction with the G(1)Pi(g) state. Band-by-band deperturbations of the G(1)Pi(g) approximately 2(1)Delta(g) (v(Pi), v(Delta)) = (11, 2), (12, 3), (15, 5), (16, 6), (18, 7), and (19, 8) bands have been performed. Deperturbed molecular constants and rotational-electronic interaction parameters are reported here. Copyright 2000 Academic Press.     

Rovibrational Intensities of the (00(0)3) <-- (10(0)0) Dyad Absorption Bands of (12)C(16)O(2)

Absolute line intensities of (12)C(16)O(2) are experimentally measured for the first time for the (00(0)3)(I) <-- (10(0)0)(II) band at 5687.17 cm(-1) and the (00(0)3)(I) <-- (10(0)0)(I) band at 5584.39 cm(-1). The spectra were obtained using a Bomem DA8 Fourier transform spectrometer and a 25-m base-path White cell at NASA-Ames Research Center. The rotationless bandstrengths at a temperature of 296 K and the Herman-Wallis parameters are S(0)(vib) = 6.68(30) x 10(-25) cm(-1)/(molecule/cm(2)); A(1) = 1.4(9) x 10(-4), and A(2) = -1.1(5) x 10(-5) for the (00(0)3)(I) <-- (10(0)0)(II) band and S(0)(vib) = 6.07(22) x 10(-25) cm(-1)/(molecule/cm(2)); A(1) = 5.2(1.5) x 10(-4) and A(2) = -4.0(7) x 10(-5) for the (00(0)3)(I) <-- (10(0)0)(I) band.     

Magnetoelectric effects in multiferroic Y-type hexaferrites Ba_(0.3)Sr_(1.7)Co_xMg_(2-x)Fe_(12)O_(22)

Y-type hexaferrites with tunable conical magnetic structures are promising single-phase multiferroics that exhibit large magnetoelectric effects. We have investigated the influence of Co substitution on the magnetoelectric properties in the Y-type hexaferrites Ba(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22)(x = 0.0, 0.4, 1.0, 1.6). The spin-induced electric polarization can be reversed by applying a low magnetic field for all the samples. The magnetoelectric phase diagrams of BaBa(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22) are obtained based on the measurements of magnetic field dependence of dielectric constant at selected temperatures. It is found that the substitution of Co ions can preserve the ferroelectric phase up to a higher temperature, and thus is beneficial for achieving single-phase multiferroics at room temperature.