N2O+经由B2Пi←X2П跃迁的光解离机理研究

在超声分子束条件下,利用360.50 nm的电离激光使N₂O分子经由[3+1]共振增强多光子电离（REMPI）产生纯净的N₂O⁺（X²Π（000））分子离子,用另一束解离激光在230-275 nm范围扫描获得N₂O⁺经由B²П_i←X²Π跃迁产生的光解碎片（NO⁺和N₂⁺）激发（PHOFEX）谱. 获得的光解碎片激发谱可以归属为B²П_i（00n）←X²Π（000）序列跃迁. 我们分别将线性三原子分子离子N₂O⁺中N―N伸缩振动简化成NO和N之间的简谐振动,N―O伸缩振动简化成N₂和O之间的简谐振动,用谐振子的简谐势能曲线和波函数对N₂O⁺分子离子X²Π和B²П_i电子态振动能级间跃迁的Franck-Condon因子进行计算,和实验得到的碎片离子增强谱实验强度进行比较,对前人给出的分子数据（分子平衡核间距）进行验证,讨论了N₂O⁺经由B²П_i（00n）←X²Π（000）电子态跃迁的光解离机理和碎片离子的分支比.     

离子速度成像在阈值光电子-光离子符合测量中的应用和改进

在阈值光电子-光离子符合质谱中, 通过增加离子检测端的电极板, 并调整相对电压形成渐增的加速电场, 获得了很好的离子速度聚焦效果. 通过这种电场, 使得具有较大平动能的离子团沿飞行方向逐渐膨胀的同时, 在垂直于飞行方向受到电场的束缚, 最终在探测器的表面实现速度聚焦, 形成缩小的图像(即速度成像的放大倍率N<1), 从而确保谱仪能够同时获得较高的平动能分辨率和质量分辨率. 应用这种缩小的速度聚焦电场, 我们研究了振动态选择的O₂ (B²Σ_g^-)离子解离动力学, 获得了碎片离子O在阈值光电子-光离子符合条件下的三维时间切片图像, 并通过比较两个解离通道所产生的O不同的平动能分布, 证实了这种离子透镜电场在较宽的离子平动能范围内能够始终保持良好的速度聚焦效果.     

离子速度成像方法研究二溴甲烷的紫外光解动力学

利用二维离子速度成像(Ion-Velocity Imaging)方法对二溴甲烷分子在234和267 nm附近的光解动力学行为进行了研究. 实验中得到了二溴甲烷光解产生的Br^*(²P_1/2)和Br(²P_3/2)在不同波长下的角度和平动能分布. 在平动能分布中发现两个高斯分布, 推测其中主要是C—Br的快速解离, 而高能宽分布则来自于CH₂Br自由基的二次解离过程. 通过角度分布得到了Br^*与Br中来自直接解离和非绝热交叉跃迁两种来源的比例. 结果表明Br^*原子主要来自于B₁态的直接解离, 而Br则绝大部分是从B₁态向A₁的非绝热交叉跃迁得到, 并导致了两种解离通道能量分布的差别.     

五氟乙烷的真空紫外光电离光解离

利用同步辐射真空紫外光电离结合飞行时间质谱对五氟乙烷(CHF₂CF₃)进行了光电离光解离的研究，测定了CHF₂CF₃的电离势及该分子主要碎片离子的出现势. 结果表明: CHF₂CF₃的绝热电离势为(12.25±0.10) eV, 主要碎片离子有CF₂CF_{3⁺、CHFCF3⁺、CF2CF2⁺、CF3⁺、CHF2⁺、CHF⁺和CF⁺，其出现势分别为 (13.93±0.10) eV, (15.25±0.10) eV, (15.12±0.10) eV, (13.30±0.05) eV, (13.05±0.08) eV, (19.17±0.10) eV和 (19.56±0.15) eV. 另外，用从头算分子轨道理论计算了解离电离过程中所有碎片的总能量，并给出了电子态及对称性. 根据实验结果和理论计算，分析了可能的解离通道，并得到了分子及母体离子的键解离能等重要的热力学数据.}     

OH自由基的高精度量子化学研究

采用内收缩MRCI方法(Internally Contracted Multiconfiguration-Reference Configuration Interaction)研究了OH自由基, 计算得到其基态稳定构型的键长是0.09708 nm, 对应的实验值是0.096966 nm, 第一激发态的键长是0.10137 nm,实验值是0.10121 nm. 同时得到势能曲线PECs (Potential Energy Curve), 再分别由Murrell-Sorbie势能函数拟合计算和POLFIT程序计算得到OH自由基在基态X²Π和第一激发态A²Σ⁺时的光谱数据：平衡振动频率ω_e, 非谐性常数ω_eχ_e以及高阶修正ω_eY_e, 平衡转动常数B_e, 振转耦合系数α_e, 解离能D₀和垂直跃迁能量ν₀₀. 这些理论计算结果与最新的实验值非常吻合, 精确度比前人也有很大提高. 其中我们计算得到基态OH(X²Π)的解离能D₀＝35568.86 cm^－1, 第一激发态OH (A²Σ⁺)的解离能D₀＝18953.93 cm^－1, 从第一激发态A²Σ⁺ (ν＝0)到基态X²Π (v＝0)的垂直跃迁能ν₀₀＝32496.42 cm^－1.     

298.15 K Li2B4O7-MgCl2-H2O体系热力学性质的电动势法测定及离子相互作用模型的研究

测定了298.15 K下, 无液接电池Li-ISE│Li₂B₄O₇ (m_A)(aq.), MgCl₂(m_B)(aq.)│AgCl/Ag的电动势, 利用测定结果计算了Li₂B₄O₇-MgCl₂-H₂O体系离子强度在0.05～3 mol•kg^－1范围内, 不同MgCl₂离子强度分数的溶液中LiCl的平均活度系数, 并给出了其随离子强度I, B₄O₇^2－和Mg^2＋浓度的变化规律. 结合以往关于该体系和Li₂B₄O₇-LiCl-H₂O, Li₂B₄O₇-H₂O体系的等压研究结果, 用迭代和多元线性回归方法对Li^＋-Mg^2＋-Cl^－-B₄O₇^2－-H₂O体系的离子相互作用模型进行了研究. 具体方法为考虑了该体系在不同的总硼浓度范围H₃BO₃, B(OH)₄^－, B₃O₃(OH)₄^－和B₄O₅(OH)₄^2－四种含硼化合物的存在以及各硼化合物间的化学平衡, 以修正了的Pitzer渗透系数方程和活度系数方程为基础, 对该体系的等压法和电动势法研究结果进行最小二乘拟合, 拟合的标准偏差为0.0167, 用该模型计算的该体系的渗透系数、活度系数与实验值基本一致.     

预处理气氛对CuO/CeO2/γ-Al2O3催化剂表面性质及“NO+CO”反应性能的影响

用不同的预处理气氛制备了CeO₂/γ-Al₂O₃载体以调节表面Ce的价态,并以Cu(CH₃COO)₂为前驱体制备了CuCeAl催化剂。XRD和H₂-TPR的结果表明在还原气氛下处理的CeO₂/γ-Al₂O₃载体具有更多的活性氧原子,因此相应的CuCeAl催化剂表面有更多分散态的Cu²⁺/Cu⁺物种。NO+CO反应的结果表明分散态的Cu²⁺/Cu⁺是NO转化的活性物质,而Cu⁰在低温下具有较好的N₂选择性。因此,同时含有分散态Cu²⁺/Cu⁺和少量晶相Cu⁰的催化剂具有最好的催化性能。     

单锰取代的Keggin型多酸吸附大气小分子X(X=H2O,N2,O2,NO,N2O,CO和CO2)的密度泛函理论计算研究

基于密度泛函理论（DFT） M06L方法对一系列单锰取代的Keggin型POM吸附大气小分子X（X=H₂O,N₂,O₂,NO,N₂O,CO和CO₂）配合物的分子几何,电子结构和成键性质进行了系统研究。由于POM的多阴离子性质,铯盐Cs₄[PW₁₁O₃₉Mn^ⅢH₂O]被用来考虑抗衡离子效应。DFT-M06L计算表明,当改变4个Cs抗衡阳离子的位置时,多酸阴离子的几何结构和电子结构参数几乎没有变化。当不考虑抗衡离子效应,在气相和溶液中单独优化多酸阴离子（[PW₁₁O₃₉Mn^ⅢH₂O]^4-）时,其主要几何和电子参数没有显著变化。比较不同自旋态的能量表明[PW₁₁O₃₉Mn^ⅡX]^4-（X=H₂O、N₂、N₂O、CO和CO₂）的最低能量态是高自旋五重态,[PW₁₁O₃₉Mn^ⅢO₂]^4-为三重态,而[PW₁₁O₃₉Mn^ⅢNO]^4-则为双重态。这些大气小分子在类卟啉POM配体上的吸附能量按照以下顺序增加：N₂ < N₂O < CO≈CO₂ < O₂ < H₂O < NO。POM-Mn-NO配合物具有较大的吸附能。Mulliken布居分析表明,NO配体与多酸中Mn^Ⅲ中心的相互作用主要来自于中间自旋态的Mn^Ⅲ中心与NO^·分子之间的反铁磁性耦合相互作用。     

298.15 K Li2B4O7-MgCl2-H2O体系热力学性质的电动势法测定及离子相互作用模型的研究

测定了298.15 K下, 无液接电池Li-ISE│Li₂B₄O₇ (m_A)(aq.), MgCl₂(m_B)(aq.)│AgCl/Ag的电动势, 利用测定结果计算了Li₂B₄O₇-MgCl₂-H₂O体系离子强度在0.05～3 mol•kg^－1范围内, 不同MgCl₂离子强度分数的溶液中LiCl的平均活度系数, 并给出了其随离子强度I, B₄O₇^2－和Mg^2＋浓度的变化规律. 结合以往关于该体系和Li₂B₄O₇-LiCl-H₂O, Li₂B₄O₇-H₂O体系的等压研究结果, 用迭代和多元线性回归方法对Li^＋-Mg^2＋-Cl^－-B₄O₇^2－-H₂O体系的离子相互作用模型进行了研究. 具体方法为考虑了该体系在不同的总硼浓度范围H₃BO₃, B(OH)₄^－, B₃O₃(OH)₄^－和B₄O₅(OH)₄^2－四种含硼化合物的存在以及各硼化合物间的化学平衡, 以修正了的Pitzer渗透系数方程和活度系数方程为基础, 对该体系的等压法和电动势法研究结果进行最小二乘拟合, 拟合的标准偏差为0.0167, 用该模型计算的该体系的渗透系数、活度系数与实验值基本一致.     

α-Fe2O3/SiO2纳米颗粒混合体系表面的酸碱性质及其对重金属离子的吸附行为

以Fe(NO₃)₃·9H₂O和正硅酸乙酯(TEOS)为原料, 通过溶胶-凝胶法和辅助模板法分别制备了纳米α-Fe₂O₃和SiO₂, 并对所合成样品进行了粉末X射线衍射(XRD)和BET表征. 使用自动电位滴定仪测定了α-Fe₂O₃/SiO₂纳米颗粒混合体系的表面酸碱性质. 研究了在不同pH下α-Fe₂O₃/SiO₂混合体系对Cu²⁺、Pb²⁺、Zn²⁺离子的吸附行为. 基于上述实验数据, 用WinSGW软件计算了α-Fe₂O₃/SiO₂混合体系表面酸碱配位常数, 并得出结论: α-Fe₂O₃/SiO₂混合体系表面反应为单一脱质子反应≡XOH ⇔ ≡XO^-+ H⁺(lg K = -8.19±0.15), 明显区别于同时具有加质子和脱质子反应的α-Fe₂O₃/SiO₂/γ-Al₂O₃, α-Fe₂O₃/γ-Al₂O₃和SiO₂/γ-Al₂O₃等纳米颗粒混合体系. 在此基础上拟合得到α-Fe₂O₃/SiO₂混合体系吸附重金属离子Cu²⁺、Pb²⁺、Zn²⁺的表面络合反应平衡常数分别为:
≡XOH + M²⁺ ⇔ ≡XOM⁺+ H⁺ [lg K = -3.1, -3.6, -3.8 (M = Cu, Pb, Zn)].
≡XOH＋M²⁺＋H₂O ⇔≡XOMOH＋2H⁺[lg K = -8.8, -8.0, -10.5 (M = Cu, Pb, Zn)]     

In situ attenuated total reflection infrared (ATR-IR) study of the adsorption of NO2-, NH2OH, and NH4+ on Pd/Al2O3 and Pt/Al2O3

In relation to the heterogeneous hydrogenation of nitrite, adsorption of NO2-, NH4+, and NH2OH from the aqueous phase was examined on Pt/Al2O3, Pd/Al2O3, and Al2O3. None of the investigated inorganic nitrogen compounds adsorb on alumina at conditions presented in this study. NO2-(aq) and NH4+(aq) on the other hand show similar adsorption characteristics on both Pd/Al2O3 and Pt/Al2O3. The vibrational spectrum of the NO2- ion changed substantially upon adsorption, clearly indicating that NO2- chemisorbs onto the supported metal catalysts. On the contrary, adsorption of NH4+ does not lead to significant change in the vibrational spectrum of the ion, indicating that the NH4+ ion does not chemisorb on the noble metal but is stabilized via an electrostatic interaction. When comparing the adsorption of hydroxylamine (NH2OH(aq)) on Pd/Al2O3 and Pt/Al2O3, significant differences were observed. On Pd/Al2O3, hydroxylamine is converted into a stable NH2(ads) fragment, whereas on Pt/Al2O3 hydroxylamine is converted into NO, possibly via HNO(ads) as an intermediate.     

利用激光诱导荧光技术研究Ca(1S0)与氯代乙烷的反应

The internal state distributions of nascent CaCl formed in the reactions Ca + (1,1) and (1,2) C_2H_4Cl_2、(1,1,2) C_2H_2Cl_3, (1,1,2,2) C_2H_2Cl_4 have been studied by means of the laser induced fluorescence (LIF) in the beam-gas apparatus. The results showed that the vibrational distributions of the CaCl products from Ca+ (1, 1) C_2H_4Cl_2. (1,1,2,2) C_2H_2Cl_4 are similar to vibrational distributions of the CaCl products from Ca + CH_2Cl_2、CHCl_3, respectively. However, the vibrational distribution of the CaCl product from Ca+(1,1,2) C_2H_3Cl_3 is equivalent to the combination of that from Ca+(1,2) C_2H_4Cl_2 and Ca+(1,1,2,2) C_2H_2Cl_4. No LIF signal has been found in the reaction Ca+(1,1) C_2H_4Cl_2.     

A study of the reaction of N+ with O2: experimental quantification of NO+(a 3Sigma+) production (298-500 K) and computational study of the overall reaction pathways

The product branching ratios for NO+(X 1Sigma+) and NO+(a 3Sigma+) produced from the reaction of N+ with O2 have been measured at 298 and 500 K in a selected ion flow tube. Approximately 0.5% of the total products are in NO+(a) at both temperatures, despite the fact that the reaction to form NO+(a) is 0.3 eV exothermic. High-level ab initio calculations of the potential energy surfaces for the N+ + O2 reaction show that the reaction from N+(3P) + O2(3Sigma(g)) reactants starts with an efficient early stage charge transfer to the N(2D) + O2+(X 2Pi) channel, which gives rise to the O2+(X 2Pi) product and, at the same time, serves as the starting point for all of the reaction channels leading to NO+ and O+ products. Pathways to produce NO+(a 3Sigma+) are found to be less favorable than pathways leading to the major product NO+(X 1Sigma+). Production of N(2D) has implications for the concentration of NO in the mesosphere.     

Dissociative photoionization of N(2)O in the region of the N(2)O(+)(B (2)Pi) state studied by ion-electron velocity vector correlation

Dissociative direct photoionization of the N2O(X 1Sigma+) linear molecule via the N2O+(B 2Pi) ionic state induced by linearly polarized synchrotron radiation P in the 18-22 eV photon energy range is investigated using the (VA+,Ve,P) vector correlation method, where VA+ is the nascent velocity vector of the NO+, N2+, or O+ ionic fragment and Ve that of the photoelectron. The DPI processes are identified by the ion-electron kinetic energy correlation, and the IchiA+(thetae,phie) molecular frame photoelectron angular distributions (MFPADs) are reported for the dominant reaction leading to NO+ (X 1Sigma+,v) + N(2D)+ e. The measured MFPADs are found in satisfactory agreement with the reported multichannel Schwinger configuration interaction calculations, when bending of the N2O+(B 2Pi) molecular ion prior to dissociation is taken into account. A significant evolution of the electron scattering anisotropies is observed, in particular in the azimuthal dependence of the MFPADs, characteristic of a photoionization transition between a neutral state of Sigma symmetry and an ionic state of Pi symmetry. This interpretation is supported by a simple model describing the photoionization transition by the coherent superposition of two ssigma and ddelta partial waves and the associated Coulomb phases.     

The vibrational state distributions in both products of the reaction: O(P) + NO2 → O2 + NO

A laser pulse-and-probe method has been used to determine the nascent vibrational populations in NO(v=0–4) and O₂(v=6–11) formed in the thermal reaction: O(³P) + NO₂ → O₂(v) + NO(v). A frequency-tripled Nd: YAG laser is used to photolyse NO₂, diluted tenfold in Ar, and laser-induced fluorescence spectroscopy in the NO A ²Σ⁺-X ²Π and O₂ B ³Σ⁻_u -X ³Σ⁻_g electronic band system is used both to follow the kinetics of individual vibrational states and to determine the nascent vibrational distributions. The majority of the NO product is formed in v = 0 and the average vibrational yield is ≈ 4.6%. The O₂ populations fall monotonically from v = 6 to 11 in a distribution close to what is expected on prior grounds. Based on a surprisal analysis, the average vibrational energy yield in O₂ is ≈ 26%. The nature of the reaction dynamics is discussed.     

Rovibrationally selected and resolved state-to-state photoionization of ethylene using the infrared-vacuum ultraviolet pulsed field ionization-photoelectron method

By preparing ethylene [C2H4(X1Ag)] in selected rotational levels of the nu11(b1u), nu2+nu12(b1u), or nu9(b2u) vibrational state with infrared (IR) laser photoexcitation prior to vacuum ultraviolet (VUV) laser photoionization, we have recorded rotationally resolved pulsed field ionization-photoelectron (PFI-PE) spectra for C2H4+(X2B3u) in the energy region of 0-3000 cm(-1) above the ionization energy (IE) of C2H4(X1Ag). Here, nu2(ag), nu9(b2u), nu11(b1u), and nu12(b1u) represent the C-C stretching, CH2 stretching, CH2 stretching, and CH2 bending modes of C2H4(X1Ag), respectively. The fully rovibrationally resolved spectra have allowed unambiguous symmetry assignments of the observed vibrational bands, which in turn have provided valuable information on the photoionization dynamics of C2H4. The IR-VUV photoionization of C2H4(X1Ag) via the nu11(b1u) or nu2+nu12(b1u) vibrational states is found to predominantly produce vibrational states of C2H4+(X2B3u) with b1u symmetry, which cannot be observed in single-photon VUV-PFI-PE measurements of C2H4(X1Ag). The analysis of the observed IR-VUV-PFI-PE bands has provided the IE(C2H4) = 84,790.2(2) cm(-1) and accurate vibrational frequencies for the nu4+(au)[84.1(2) cm(-1)], nu12+(b1u)[1411.7(2) cm(-1)], nu4+ +nu12+(b1g)[1482.5(2) cm(-1)], nu2+(ag)[1488.3(2) cm(-1)], nu2+ + nu4+(au)[1559.2(2) cm(-1)], 2nu4+ + nu12 +(b1u)[1848.5(2) cm(-1)], 4nu4+ + nu12 +(b1u)[2558.8(2) cm(-1)], nu2+ + nu12 +(b1u)[2872.7(2) cm(-1)], and nu11+(b1u)[2978.7(2) cm(-1)] vibrational states of C2H4+(X2B3u), where nu4+ is the ion torsional state. The IE(C2H4) and the nu4+(au), nu2+(ag), and nu2+ + nu4+ (au) frequencies are in excellent accord with those obtained in previous single-photon VUV-PFI-PE measurements. The other ion vibrational frequencies represent new experimental determinations. We have also performed high-level ab initio anharmonic vibrational frequency calculations for C2H4(X1Ag) and C2H4+(X2B3u) at the CCSD(T)/aug-cc-pVQZ level for guidance in the assignment of the IR-VUV-PFI-PE spectra. All theoretical vibrational frequencies for the neutral and ion, except the ion torsional frequency, are found to agree with experimental vibrational frequencies to better than 1%.     

Model systems for probing metal cation hydration: the V+(H2O) and ArV+(H2O) complexes

In support of mass-selected infrared photodissociation (IRPD) spectroscopy experiments, coupled-cluster methods including all single and double excitations (CCSD) and a perturbative contribution from connected triple excitations [CCSD(T)] have been used to study the V+(H2O) and ArV+(H2O) complexes. Equilibrium geometries, harmonic vibrational frequencies, and dissociation energies were computed for the four lowest-lying quintet states (5A1, 5A2, 5B1, and 5B2), all of which appear within a 6 kcal mol(-1) energy range. Moreover, anharmonic vibrational analyses with complete quartic force fields were executed for the 5A1 states of V+(H2O) and ArV+(H2O). Two different basis sets were used: a Wachters+f V[8s6p4d1f] basis with triple-zeta plus polarization (TZP) for O, H, and Ar; and an Ahlrichs QZVPP V[11s6p5d3f2g] and Ar[9s6p4d2f1g] basis with aug-cc-pVQZ for O and H. The ground state is predicted to be 5A1 for V+(H2O), but argon tagging changes the lowest-lying state to 5B1 for ArV+(H2O). Our computations show an opening of 2 degrees -3 degrees in the equilibrium bond angle of H2O due to its interaction with the metal ion. Zero-point vibrational averaging increases the effective bond angle further by 2.0 degrees -2.5 degrees, mostly because of off-axis motion of the heavy vanadium atom rather than changes in the water bending potential. The total theoretical shift in the bond angle of about +4 degrees is significantly less than the widening near 9 degrees deduced from IRPD experiments. The binding energies (D0) for the successive addition of H2O and Ar to the vanadium cation are 36.2 and 9.4 kcal mol(-1), respectively.     

State-selective preparation of NO2+ and the effects of NO2+ vibrational mode on charge transfer with NO

Two color resonance-enhanced multiphoton ionization (REMPI) scheme of NO(2) through the E (2)Sigma(u)(+) (3psigma) Rydberg state was used to prepare NO(2)(+) in its ground and (100), (010), (02(0)0), (02(2)0), and (001) vibrational states. Photoelectron spectroscopy was used to verify >96% state selection purity, in good agreement with results of Bell et al. for a similar REMPI scheme. The effects of NO(2)(+) vibrational excitation on charge transfer with NO have been studied over the center-of-mass collision energy (E(col)) range from 0.07 to 2.15 eV. Charge transfer is strongly suppressed by collision energy at E(col) < approximately 0.25 eV but is independent of E(col) at higher energies. Mode-specific vibrational effects are observed for both the integral and differential cross-sections. The NO(2)(+) bending vibration strongly enhances charge transfer, with enhancement proportional to the bending quantum number, and is not dependent on the bending angular momentum. The enhancement results from increased charge transfer probability in large impact parameter collisions that lead to small deflection angles. The symmetric stretch also enhances reaction at low collision energies, albeit less efficiently than the bend. The asymmetric stretch has virtually no effect, despite being the highest-energy mode. A model is proposed to account for both the collision energy and the vibrational state dependence.     

Experimental Study of C2Cl3+NO2 Reaction

The free radical reaction of C2Cl3 with NO2 was investigated by step-scan time-resolved FTIR (TR-FTIR) emission spectroscopy. Due to the vibrationally excited products of Cl2CO, NO, and CO, strong IR emission bands were observed with high resolution TR-FTIR spectra. Four reaction channels forming C2Cl3O+NO, CCl3CO+NO, CO+NO+CCl3, and ClCNO+Cl2CO were elucidated, respectively. Spectralˉtting showed that the product CO was highly vibrationally excited with the nascent average vibrational energy of 60.2 kJ/mol. Possible reaction mechanism via intermediates C2Cl3NO2 and C2Cl3ONO was proposed.     

Inversion vibration of PH3+(X2A2") studied by zero kinetic energy photoelectron spectroscopy

We report the first rotationally resolved spectroscopic studies on PH3+(X2A2") using zero kinetic energy photoelectron spectroscopy and coherent VUV radiation. The spectra about 8000 cm(-1) above the ground vibrational state of PH3+(X2A2") have been recorded. We observed the vibrational energy level splittings of PH3+(X2A2") due to the tunneling effect in the inversion (symmetric bending) vibration (nu2+). The energy splitting for the first inversion vibrational state (0+/0-) is 5.8 cm(-1). The inversion vibrational energy levels, rotational constants, and adiabatic ionization energies (IEs) for nu2+ = 0-16 have been determined. The bond angles between the neighboring P-H bonds and the P-H bond lengths are also obtained using the experimentally determined rotational constants. With the increasing of the inversion vibrational excitations (nu2+), the bond lengths (P-H) increase a little and the bond angles (H-P-H) decrease a lot. The inversion vibrational energy levels have also been calculated by using one dimensional potential model and the results are in good agreement with the experimental data for the first several vibrational levels. In addition to inversion vibration, we also observed firstly the other two vibrational modes: the symmetric P-H stretching vibration (nu1+) and the degenerate bending vibration (nu4+). The fundamental frequencies for nu1+ and nu4+ are 2461.6 (+/-2) and 1043.9 (+/-2) cm(-1), respectively. The first IE for PH3 was determined as 79670.9 (+/-1) cm(-1).