交叉分子束研究氟原子与1,2-丁二烯反应动力学

利用通用型交叉分子束研究了氟原子与1,2-丁二烯的反应,观测到了C₄H₅F+H反应通道. 测量产物C₄H₅FF在实验坐标下的角度分辨的飞行时间谱,获得了这个通道质心坐标下的产物角分布和动能分布. 实验结果表明,相对于氟原子束方向,产物C₄H₅FF主要是后向散射,同时也有大量的前向散射. 这表明反应通道主要通过长寿命的络合物形成机理进行的,同时也伴有直接的双分子亲核取代反应(SN2)机理.     

F+H2O/D2O→HF+OH反应的准经典轨迹研究：能垒、反应物转动激发和同位素取代的影响 (cited: 4)

在新构建的含旋轨耦合校正的FH₂O基态势能面上,采用准经典轨迹方法详细研究了F+H₂O/D₂O→HF/DF+OH/OD的反应动态学．氢和氘抽取反应经过较低的类反应物过渡态直接发生反应,生成振动激发的HF/DF和内能较低的OH/OD产物．由于新构建的势能面能垒较低,得到的积分反应截面与实验值吻合．但新势能面对产物态分布和模式选择性影响较小．理论计算结果显示H2O的转动态激发对反应有很强的促进作用,说明其与反应坐标耦合紧密．     

OH+H2S→H2O+SH反应的模式特异性量子动力学研究

研究氢抽取反应OH+H₂S对于理解酸雨形成、空气污染和气候变化的原因具有重要意义. 本文在降维模型下使用量子含时波包方法研究了OH+H₂S→H₂O+SH反应的动力学行为. 研究表明，该反应在低碰撞能时表现出无垒反应的特征，而在高碰撞能下表现出具有显著势垒的激活反应的特征. 激发反应物H₂S分子的对称或反对称伸缩模式比激发弯曲模式更有效地促进了反应，该动力学特征可以通过各正则模式与反应坐标的耦合强度来解释. 此外，模式指定的反应速率常数表现出明显的非阿伦尼乌斯温度依赖性.     

对典型多通道反应H+CH3OH的模式特异动力学研究

H+CH₃OH作为典型的多通道反应,在燃烧和星际中起着重要的作用. 本文基于在UCCSD(T)-F12a/AVTZ水平上计算的大量数据点,构建了该体系的全维精确势能面,并基于该势能面,研究了不同产物通道的模式特异动力学. 结果表明,O-H 伸缩、沿C-O轴的扭转以及C$-$H伸缩等模式的振动激发对H₂+CH₃O、H₂+CH₂OH、H₂O+CH₃和H+CH₃OH四个产物通道有着不同的影响. 该研究有助于理解具有多个产物通道的复杂反应的模式特异动力学,进而帮助控制其竞争反应.     

气相中自由基OH在不同催化剂下对甲酰氟FCHO进行提氢反应的理论性研究

分别在水、甲酸和硫酸存在的情况下,通过CCSD(T)//M06-2X/6-311++G(3df,3pd)的理论方法,对大气中自由基OH提取甲酰氟FCHO上的氢进行了反应机理和动力学的研究.计算结果表明相对于反应物,加入催化剂的过渡态的能垒从3.64 kcal/mol分别下降到-2.89、-6.25和-7.76 kcal/mol,表明水、甲酸和硫酸在甲酰氟FCHO和自由基OH提氢反应中起了重要作用.通过运用具有Eckart隧道校正的传统过渡态理论计算出的动力学数据表明通道X...FCHO+OH(X=H₂O, HCOOH,或者H₂SO₄)要比通道X...OH+FCHO更有利于反应的发生.催化剂水、甲酸和硫酸的加入使甲酰氟FCHO 和自由基OH提氢反应的速率常数要比不加催化剂时小,说明了催化剂的加入不能促进大气中甲酰氟FCHO和自由基OH的反应.     

在水-四氢呋喃中纤维素转化为5-羟甲基糠醛及副产物鉴定

在酸性条件下,水-四氢呋喃混合溶剂中转化纤维素制备了平台化合物5-羟甲基糠醛(HMF)．在纤维素浓度仅为2.4wt%时,可以得到38.6%的HMF,但是随着纤维素浓度的增加,胡敏素和乙酰丙酸成为主要产物．利用液相色谱-多级串联质谱联用技术检测到了分子式为C₉H₁₆O₄、 C₁₀H₁₄O₄、 C₁₁H₁₂O₄、C₁₂H₁₀O₅ 和C₁₂H₁₆O₈的一系列副产物．C₉H₁₆O₄是通过四氢呋喃开环为1,4-丁二醇再与乙酰丙酸酯化反应得到,而C₁₀H₁₄O₄是通过四氢呋喃开环后与HMF醚化得到．C₁₁H₁₂O₄是由5-羟甲基糠醛与乙酰丙酸发生酯化反应得到,C₁₂H₁₀O₅是由HMF自身醚化得到,而C₁₂H₁₆O₈是HMF与葡萄糖经过缩醛反应得到．HMF的自身醚化反应及HMF与1,4-丁二醇的醚化反应是主要的副反应．     

环戊酮光电离解离的实验和理论研究

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程. 在9.0∽15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线. 通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03 eV,并确认碎片离子为：C₅H₇O⁺,C₄H₅O⁺,C₄H₈⁺,C₃H₃O⁺,C₄H₆⁺,C₂H₄O⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺,C₂H₅⁺, C₂H₄⁺. 利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C₅H₈O⁺的解离机制. 通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

异戊二烯解离光电离理论研究

利用CBS-QB3理论计算方法研究了异戊二烯的可能解离通道.获得了主要碎片离子C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺的C₂H₃⁺的结构以及这些解离通道的解离能,并给出了相应的过渡态和中间体的结构和位垒.得到的异戊二烯电离势及主要碎片离子的出现势均与实验值符合的较好.最后,通过理论和实验结果的对比讨论了各通道的解离机理.     

硫酸催化乙二醛气体相水化反应机理和速率常数理论计算研究

采用M06-2X和CCSD(T)高阶量化计算和传统过渡态理论研究硫酸催化乙二醛气体相水化反应.对HCOCHO+H₂O, HCOCHO+H₂O+H₂O, HCOCHO+H₂O+H₂O, HCOCHO+H₂O...H₂SO₄和HCOCHO+H₂O+H₂SO₄五个路径的反应机理和速率常数进行了研究.计算结果表明硫酸具有较强的催化能力,能显著减小乙二醛水化反应的能垒,在CCSD(T)/6-311++G(3df,3pd)//M06-2X/6-311++G(3df,3pd)理论水平,当硫酸分子参与乙二醛水化反应时,反应能垒从37.15 kcal/mol减少至7.08 kcal/mol.在室温条件下,硫酸催化乙二醛水化反应的反应速率1.34×10^-11 cm³/(molecule.s),是等量水分子参与乙二醛水化反应的速率的10¹²倍,大于乙二醛与OH自由基反应的反应速率1.10×10^-11 cm³/(molecule.s).这表明大气条件下,硫酸催化乙二醛水化反应可以发生,同乙二醛与OH自由基反应相竞争.     

甲基环己烷在9∽15.5 eV能量区的真空紫外光电离研究

利用具有同步辐射源的反射式飞行时间质谱仪,研究甲基环己烷的真空紫外光电离和光解离. 观测到母体离子C₇H₁₄⁺和碎片离子C₇H₁₃⁺,C₆H₁₁⁺,C₆H₁₀⁺,C₅H₁₀⁺,C₅H₉⁺,C₄H₈⁺,C₄H₇⁺和C₃H₅⁺的光电离效率曲线. 测定甲基环己烷的电离能为9.80±0.03 eV,通过光电离效率曲线确定其碎片离子的出现势. 在B3LYP/6-31G(d)水平上对过渡态、中间体和产物离子的优化结构进行表征,并使用G3B3方法计算其能量. 提出主要碎片离子的形成通道. 分子内氢迁移和碳开环是甲基环己烷裂解途径中最重要的过程.     

Molecular dynamics study of the reaction C<Subscript>3</Subscript> + H <Subscript>3</Subscript><Superscript>+</Superscript>

Both a quantum molecular dynamic method and high level ab initio calculations (MP2, CCSD(T)) have been used to investigate the mechanism of the C₃ + H₃⁺ reaction, which is part of the ion chemistry in interstellar clouds. Furthermore statistic initial orientations in collision simulations have been set up in order to determinate reaction cross-sections and rate coefficients of all occurring reaction channels. Our analysis shows that the revealed mechanism is strongly determined by dynamic effects.     

Potential Energy Surface for Oxidation of Indenyl C<Subscript>9</Subscript>H<Subscript>7</Subscript>

Ab initio calculations were performed to obtain local energy extrema, including an effect of reagents, intermediates, and reaction products on the potential energy surface for the C₉H₇+O₂ reaction, playing a significant role in oxidation of polycyclic aromatic hydrocarbons at combustion conditions. The final products, determined as a result of the calculations are styrenyl radical C₈H₇+CO₂, ortho-vinyl phenyl radical C₈H₇+CO₂ and 1-H-inden-1-one C₉H₆O+OH, which is predicted to be the prevailing reaction product.     

Theoretical kinetics of HO2 + C5H5: A missing piece in cyclopentadienyl radical oxidation reactions

The resonantly-stabilized cyclopentadienyl radical (C₅H₅) is a key species in the combustion and molecular growth kinetics of mono and poly-aromatic hydrocarbons (M/PAHs). At intermediate-to-low temperatures, the C₅H₅ reaction with the hydroperoxyl radical (HO₂) strongly impacts the competition between oxidation to smaller products and growth to PAHs, precursors of soot. However, literature estimates for the HO₂ + C₅H₅ reaction rate are inaccurate and inconsistent with recent theoretical calculations, thus generating discrepancies in global combustion kinetic models. In this work, we perform state-of-the-art theoretical calculations for the HO₂ + C₅H₅ reaction including variable reaction coordinate transition state theory for barrierless channels, accurate thermochemistry, and multi-well master equation (ME) simulations. Contrary to previous studies, we predict that OH + 1,3-C₅H₅O is the main reaction channel. The new rate constants are introduced in two literature kinetic models exploiting our recently developed ME based lumping methodology and used to perform kinetic simulations of experimental data of MAHs oxidation. It is found that the resonantly-stabilized 1,3-C₅H₅O radical is the main C₅H₅O isomer, accumulating in relevant concentration in the system, and that the adopted lumping procedure is fully consistent with results obtained with detailed kinetics. The reactivity of C₅H₅O with OH and O₂ radicals is included in the kinetic mechanisms based on analogy rules. As a result, C₅H₅O mostly reacts with O₂ producing smaller C₃/C₄ species and large amounts of C₅H₄O, suggesting that further investigations of the reactivity of both C₅H₅O and C₅H₄O with oxygenated radicals is necessary. Overall, this work presents new reliable rate constants for the HO₂ + C₅H₅ reaction and provides indications for future investigations of relevant reactions in the sub-mechanisms of cyclopentadiene and MAH oxidation.     

Optimized semiempirical potential energy surface for H<Subscript>2</Subscript><Superscript>16</Superscript>O up to 26000 cm<Superscript>−1</Superscript>

A semiempirical potential energy surface is obtained for the major isotopologue of the water molecule H₂ ¹⁶O that allows the vibration-rotation energy levels in the range of 0–26000 cm⁻¹ to be calculated with an accuracy almost equal to the average experimental accuracy of measurements in the infrared and visible ranges. Variational calculations using this potential energy surface reproduce the experimental energy values of more than 1500 vibration-rotation levels of H₂ ¹⁶O with the total angular momentum quantum number J = 0, 2, and 5 in the indicated range with a standard deviation of 0.022 cm⁻¹. The potential was obtained by optimizing a starting ab initio surface using a combination of two approaches, i.e., (1) the multiplication of the starting ab initio surface by a morphing function whose parameters were optimized and (2) the optimization of parameters of the ab initio surface using both the experimental values of energy levels and the results of quantum-chemical electronic structure calculations.     

Coupled ab initio potential energy surfaces for the two lowest 2A′ electronic states of the C2H molecule

Realistic two-valued potential energy surfaces for the reaction C(³P) + CH(X²Π) → C₂ + H have been constructed from a set of high level ab initio data describing the first two ²A′ electronic states of the C₂H system. These states have linear equilibrium configurations, known as the X ²Σ⁺ and A²Π states, and are coupled by a conical intersection. They lead to the formation of C₂(X¹Σ⁺ _g) and C₂(a³Π_u) considering an adiabatic dissociation process. The ab initio calculations are of the multireference configuration interaction variety and were carried out using a polarized triple-zeta basis set. Using the ab initio adiabatic energies and the matrix elements of the dipole moment, a 2 × 2 diabatic representation of the electronic Hamiltonian was built. Each element of this Hamiltonian matrix was expressed within the double many-body expansion (DMBE) scheme which is based, in this case, on the extended Hartree-Fock approximate correlation energy model (EHFACE). The analytical adiabatic potential energy surfaces are then obtained as the eigenvalues of this matrix, and display correctly the Σ/Π conical intersection. Moreover, the non-adiabatic couplings given by our analytical model are compared with the ab initio ones, and good qualitative agreement is observed.     

Anatomy of relativistic energy corrections in light molecular systems

Relativistic energy corrections which arise from the use of the Dirac-Coulomb Hamiltonian, and the Gaunt and Breit interaction operators, plus Lamb-shift effects have been determined for the global minima of the ground electronic states of C₂H₆, NH₃, H₂O, [H,C,N], HNCO, HCOOH, SiC₂, SiH^? ₃, and H₂S, and for barrier characteristics for these molecular systems (inversion barrier of NH₃ and SiH^? ₃, barrier to linearity of H₂O, H₂S, and HNCO, rotational barrier of C₂H₆, difference between conformations of HCOOH (Z/E) and SiC₂ (linear/T-shaped), and isomerization barrier of HCN/HNC). The relativistic calculations performed at the Hartree-Fock and the highly correlated CCSD(T) levels employed a wide variety of basis sets. Comparison of the perturbational and the four-component fully variational results indicate that the Coulomb-Pauli Hamiltonian and the lowest order Hamiltonian of direct perturbation theory (DPT(2)) are highly successful for treating the relativistic energy effects in light molecular systems both at a single point on the potential energy hypersurface and along the surface. Electron correlation contributions to the relativistic corrections are relatively small for the systems studied, and are comparable with the 2-electron Darwin correction. Corrections beyond the Dirac-Coulomb treatment are usually rather small, but may become important for high accuracy ab initio calculations.     

Kinetic energy of structural protons in silica xerogels

The kinetic energies of the protons in the silanol groups (Si–OH units) of silica xerogels were deduced by ab initio calculations using the basis set mp2/6-311G**. The silanol groups were simulated using the Si(OH)₄ unit. The calculated result of the H-kinetic energy was found to be 150 meV, which is ~ 50% smaller than a recently reported experimental value for porous silica xerogels. For comparison, the same calculations of the proton kinetic energies of other H-containing molecules such as H₂O and CH₄ (being also ~ 150 meV) were found to be in excellent agreement with measurements. Possible reasons for the huge deviations in the case of the silanols are discussed.     

Organic compounds in the C3H6O3 family: Microwave spectrum of cis-cis dimethyl carbonate

Geometry optimization calculations on 13 members of the C₃H₆O₃ family of organic species have been carried out to determine their relative binding energies. Dimethyl carbonate [(CH₃)₂CO₃] is one of the lower energy species in this family, which includes the C₃-sugars 1,3-dihydroxyacetone and glyceraldehyde. The microwave spectrum of dimethyl carbonate has been measured over the frequency range 8.4-25.3 GHz with several pulsed-beam Fourier-transform microwave spectrometers and from 227 GHz to 350 GHz with direct absorption spectrometers. The spectrum of the lowest-energy cis-cis conformer of dimethyl carbonate has been assigned, and ab initio electronic structure calculations of the three possible conformers have been performed. Stark effect measurements were carried out on the cis-cis conformer to provide accurate determinations of the dipole moment components.     

Ab initio potential energy curves and vibrational levels for the C and D 1Πu states of the hydrogen molecule

Two lowest eigenvalues of the Hamiltonian for the hydrogen molecule corresponding to the ¹Π_u symmetry have been calculated in the Born-Oppenheimer approximation. They represent the C and D states, respectively. Different highly flexible wavefunctions were used for both states and the calculations were performed for a wide range of internuclear distances: 1 ≤ R ≤ 12 a.u. for the C state, and 1 ≤ R ≤ 25 a.u. for the D state. The calculated potential energy curves are more accurate than any previous ab initio results for the above states. The vibrational Schrödinger equation for both states has been solved for H₂, HD, and D₂ using the Numerov method. The resulting energies and rotational constants are compared with the experimental values.     

Accurate ab initio-based DMBE potential energy surface for HLi2(X 2A′) via scaling of the external correlation

A globally accurate potential energy surface is reported for the electronic ground-state HLi₂ by fitting ab initio energies to double many-body expansion formalism. The total 3726 ab initio energies used to map the HLi₂ potential energy surface are calculated using the multi-reference configuration interaction method, with their dynamical correlation being semiempirically corrected by the double many-body expansion-scaled external correlation method. The current potential energy surface generates an excellent fit of the ab initio energies, showing a small root-mean squared derivation of 0.636 ? kcal ? mol^-1. The topographical features of the HLi₂ potential energy surface are examined in detail, which concludes that the H + Li₂(X ? ¹ Σ _g ) → Li + LiH(X ? ¹ Σ) reaction is essentially barrierless and the exothermicity is calculated to be 33.668 ? kcal ? mol^-1, thus corroborates the available experimental and theoretical results.