CO(υ)高振动激发态向C_2H_2的振动传能研究

用时间分辨窝里叶红外发射谱研究了高振动激发态CO向C2H2的传能，得到了CO（v＝1－3）各振动态布展及其随时间的变化,利用微分法解出弛豫微分方程组，获得CO（v=1-3）向C2H2的传能速率常数分别为：2．0±0．1，6.0±0．2和9．1±0.8（10-13cm3·molecule-1·s-1）．传能速率随着振动量子数的增加而迅速增加．CO的振动能应向C2H2的对称伸缩模v2近共振V－V传递．传能过程中还可能形成二聚体络合物，加速了CO（v）向C2H2的传能．用abinitio方法确定了CO...C2H2两种可能的直线构型．     

CO(υ)高振动激发态向C2H2的振动传能研究

用时间分辨富里叶红外发射谱研究了高振动激发态ＣＯ向Ｃ２Ｈ２的传能，得到了ＣＯ（ｖ＝１－３）各振动态布居及其随时间的变化。利用微分法解出弛豫微分方程组，获得ＣＯ（ｖ＝１－３）向Ｃ２Ｈ２的传能速率常数分别为：２．０±０．１，６．０±０．２和９．４±０．８（１０＾－１３ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１·ｓ＾－１）。传能速率随着振动量子数的增加而迅速增加。ＣＯ的振动能应向Ｃ２Ｈ２的对称伸缩模ｖ２近共振Ｖ－     

New ab initio potential energy surfaces for both the ground (X̃1A') and excited (Ã1A″) electronic states of HSiCl and the absorption and emission spectra of HSiCl/DSiCl

New ab initio potential energy surfaces for the ground ( ) and excited ( ) electronic states of HSiCl were obtained by using the single and double excitation coupled‐cluster theory with a noniterative perturbation treatment of triple excitations and the multi‐reference configuration interaction with Davidson correction, respectively, employing an augmented correlation‐consistent polarized valence quadruple zeta basis set. For the excited state , an extended active space (18 electrons in 12 orbitals) was used. The calculated vibrational energy levels of HSiCl and DSiCl of the ground and excited electronic states are in better agreement with the available experimental values than the previous theoretical results. In addition, with the calculated transition dipole moment, the absorption and emission spectra of HSiCl and DSiCl were calculated using an efficient single Lanczos propagation method and are in reasonable agreement with the available observed spectra. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Potential energy surfaces and vibrational spectra for isotopomers of N_2O

ＴｈｅＮ2Ｏｍｏｌｅｃｕｌｅｐｌａｙｓａｖｅｒｙｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｏｚｏｎｅｃｈｅｍｉｓｔｒｙｉｎｔｈｅａｔｏｍｏｓｐｈｅｒｅ.Ｉｔｓｒｏｖｉｂｒａｔｉｏｎａｌｓｐｅｃｔｒａｃａｎｐｒｏｖｉｄｅｕｓｅｆｕｌｉｎｆｏｒｍａｔｉｏｎａｂｏｕｔｔｈｅｉｎｔｒａｍｏｌｅｃｕｌａｒｄｙｎａｍｉｃｐｒｏｐｅｒｔｉｅｓ.Ｎ2Ｏｉｓａｌｉｎｅａｒｍｏｌｅｃｕｌｅａｔｔｈｅｅｑｕｉｌｉｂｒｉｕｍｇｅｏｍｅｔｒｙｆｏｒｔｈｅｅｌｅｃｔｒｏｎｉｃｇｒｏｕｎｄｓｔａｔｅ.Ｎｕｍｅｒｏｕｓｉｎｖｅｓｔｉｇａｔｉｏ…     

Vibrational intensities of liquid N-methylpiperidine

Thin film transmission spectra of liquid N-methylpiperidine were measured in the 4000–500 cm⁻¹ region, using cells of thicknesses ranging from 1 to 8.2 μm. The spectra of both components of the complex refractive index were determined from these data in the mid-IR. Vibrational intensities and other spectral data were calculated from the k(ν) spectrum. In this region 41 bands were detected and quantitatively described. The assignment of numerous bands was carried out. The results were compared with available literature data.     

Theoretical Studies on the Potential Energy Surface and Vibrational Energy Levels of HXeBr

The potential energy surface for the electronic ground state of the HXeBr molecule is constructed from more than 4200 ab initio points calculated using the internally contracted multi-reference configuration interaction method with the Davidson correction （icMRCI ＋ Q）. The stabilities and dissociation barriers are identified from the potential energy surface. The three-body dissociation channel is found to be the dominant dissociation channel for HXeBr. Low-lying vibrational energy levels of HXeBr calculated using the Lanczos algorithm are found to be in good agreement with the available experimental band origins.     

Multireference configuration interaction study on spectroscopic parameters and molecular constants of PO and PO+

The highly accurate valence internally contracted multireference configuration interaction (MRCI) approach has been employed to investigate the potential energy curves (PECs) for the X²Π, b⁴Σ^?, C²Σ^? states of PO and the X¹Σ⁺ state of PO⁺. For these electronic states, the spectroscopic parameters of the isotopes (P¹⁶O, P¹⁸O, P¹⁶O⁺, and P¹⁸O⁺) have been determined and compared with those of the investigations reported in the literature. The comparison shows that excellent agreement exists between the present results and the available experiments. With the PECs determined here, the first 30 vibrational states for P¹⁶O(X²Π, b⁴Σ^?), P¹⁸O(X²Π, b⁴Σ^?), P¹⁶O⁺(X¹Σ⁺), and P¹⁸O⁺(X¹Σ⁺) are computed when the rotational quantum number J equals zero (J = 0). The vibrational level G(υ), inertial rotation constant B_υ and centrifugal distortion constant D_υ are determined when J = 0. All the results of vibrational states except for P¹⁶O (X²Π) are reported for the first time. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

The surface potential of solvent and the intraphase pre-existing potential

Using own and literature data, the differences of real solvation energy for ferricenium and ferrocene in six solvents are found. These quantities are confronted with the calculated difference of the dielectric response energies plus nonelectrostatic energies for the redox couple. Such a comparison allows determining the sum of the surface and intraphase potentials. The comparison of these sums with the experimental values of the surface potential differences obtained by the measuring of Volta potentials allowed determining the differences of pre-existing intraphase potentials formed by solvent molecules on the ferrocene molecule. Thus, the intraphase potentials are evaluated for the first time, using an approach not based on the molecular-dynamic modeling. Using some approximations, the surface potentials of the studied solvents are found.     

Simple molecular wavefunctions with correlation corrections II

The potential curves for the ground state of Li₂ (¹ _g ⁺ ) and FH (¹ _g ⁺ ) are computed. The correlation energy is calculated using a functional of the one- and two-electron density matrices derived from an MC SCF reference wavefunction and is added to the reference energy to obtain a correlated potential curve.     

十九种长链正烷基脂肪酸的碳链骨架振动能量研究

本文通过红外光谱(FT-IR)测量数据和预测数据,计算与研究了十九种长链正烷基脂肪酸(简称脂肪酸或碳酸)的碳链骨架振动能量。结果显示出脂肪酸的碳链骨架振动能量随碳数增加呈阶梯状关系,而且脂肪酸的碳链骨架振动能量∑E出现奇偶数更迭规律。此结果可用来解释脂肪酸的熔点或熔化热呈现奇偶数更迭现象。