共查询到20条相似文献,搜索用时 15 毫秒
1.
We measure the dispersed spectrum of the A2Π~X2Σ+ system of MgH using laser abla-tion/laser induced Fluorescence method and obtain the Frank-Condon factors and related transition frequencies of the A2Π(v′=0)-X2Σ+(v〞=0,1) system by analyzing the experimen-tal spectrum. Also, we calculate the Franck-Condon factors and transition frequencies of the A2Π~X2Σ+ system of MgH. A comparison of our theoretical calculation and experimental results with other reported theoretical results was carried out as well. 相似文献
2.
The laser-induced fluorescence excitation spectrum of CoC was recorded in the spectral region from 13500 cm-1 to 22000 cm-1, in which the CoC molecules were produced by the reaction of sputtered cobalt atoms with methanol under supersonic jet cooled conditions. Much of the visible spectrum was assigned to transitions between the X2∑+ ground state and F2∑+ state. The 11 bands assigned as (v’=3-13, 0) transitions of the F2∑+- X2∑+ band system were observed and rotationally analyzed. Equilibrium constants for the F2∑+ state were Te=1362 cm-1, ωe=669 cm-1 ,ωe?e=4.3 cm-1, Be=0.546 cm-1, and Re=1.758A. Some new bands were observed. 相似文献
3.
贫氢分子CnH是燃烧火焰、行星大气中的重要的中间体.这些分子与其它一些分子或自由基的反应在星际化学中起着非常重要的作用.虽然这些分子的电子结构和光谱性质已经进行了广泛的研究,但是研究这些反应的机理和动力学性质也是亟需的.因此,我们采用直接动力学方法对线性分子丁二炔自由基C4H(CCCCH)夺氢气(H2)分子中HAT的反应的微观机理和动力学性质进行了理论研究.本研究分别在BB1K/6-311+G(2d,2p),B3LYP/6-311+G(2d,2p)和M06-2x/6-311+G(2d,2p)水平上优化得到了各稳定点的结构及振动频率.为了得到更为可靠的反应能量和势能面信息,在BB1K/6-311+G(2d,2p)优化结构的基础上用CCSD(T)/aug-cc-pVTZ水平进行了单点能量校正.对于此反应研究了两条不同的氢吸附通道,C4H(C1C2C3C4H)中的C1和C4分别吸氢,即通道1(R1)和通道2(R2).计算得出:通道1和通道2的能垒分别为3.58 kcal/mol和26.56 kcal/mol,结果表明C4H中C1端吸氢是主要通道.反应过程中的电子转移可以为理解氢原子转移(HAT)提供重要的线索,因此,我们利用NBO对反应过程中的电子转移行为进行了详细的分析.本工作运用经典过渡态理论(VTST)与变分过渡态理论(CVT)和变分过渡态理论结合小曲率隧道效应校正(CVT/SCT)的方法计算了该反应在40~1000 K温度区间的速率常数.除对于最低频率的配分函数采用了阻尼内转动近似外,其它频率都采用谐振子模型处理.计算得到的总的CVT/SCT反应速率常数与已有的实验值符合得很好.我们还提供了40~1000K温度范围内的三参数Arrhenius表达式.这些公式有利于今后在较宽的温度范围内迄今没有实验数据的反应的研究. 相似文献
4.
High Resolution Laser Excitation Spectra and Franck-Condon Factors of A2Π-X2Σ+ Electronic Transition of MgF
下载免费PDF全文
![点击此处可从《化学物理学报(中文版)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Jingwang Gu Zengjun Xiao Chunting Yu Qiang Zhang Yang Chen Dongfeng Zhao 《化学物理学报(中文版)》2022,35(1):58-68
Magnesium monofluoride (MgF) is proposed as an ideal candidate radical for direct laser cooling. Here, the rotationally resolved laser spectra of MgF for the A2Π-X2Σ+ electronic transition system were recorded by using laser induced fluorescence technique. The MgF radicals were produced by discharging SF6/Ar gas mixtures between the tips of two magnesium needles in a supersonic jet expansion. We recorded a total of 19 vibrational bands belonging to three sequences of Δv=0, ±1 in the region of 348-370 nm. Accurate spectroscopic constants for both X2Σ+ and A2Π states are determined from rotational analysis of the experimental spectra. Spectroscopic parameters, including the Franck-Condon factors (FCFs), are determined from the experimental results and the Rydberg-Klein-Rees (RKR) calculations. Significant discrepancies between the experimentally measured and RKR-calculated FCFs are found, indicating that the FCFs are nearly independent of the spin-orbit coupling in the A2Π state. Potential energy curves (PECs) and FCFs determined here provide necessary data for the theoretical simulation of the laser-cooling scheme of MgF. 相似文献
5.
Qingyong Meng Hai-Bo Chang Ming-Bao Huang Hua Dong 《Theoretical chemistry accounts》2011,128(3):359-365
The N-loss predissociation mechanisms of the A 2Σ+ (2 2
A′) state of N2O+ to the first and second dissociation limits were studied in the C
s symmetry. The potential energy curves (PECs) and minimum energy crossing points (MECPs) for the C
s states of N2O+ were calculated at the CAS levels. On the basis of our CAS calculation results (CASPT2 energetic results and CASSCF spin
orbit couplings), we suggest two processes for N-loss predissociation mechanisms of A 2Σ+ (2 2
A′) to the first and second limits. The first two steps in the two processes are the same: A 2Σ+ passes through the 2 2
A′/1 4
A″ MECP and then reaches the 1 4
A″ (1 4Σ−) PEC. The 2 2
A′/1 4
A″ MECP has a bent geometry and is slightly higher in energy than the transition state along the 1 4
A″ PEC. Our mechanisms are different from the previously suggested mechanisms (via 1 4Π). 相似文献
6.
V. V. Sharutin V. S. Senchurin O. K. Sharutina B. B. Kunkurdonova 《Russian Journal of Inorganic Chemistry》2011,56(9):1384-1389
Complexes [Me3EtN]2+[CoI4]2− (I) and [Me3EtN]2+[CoI4]2− (II) were synthesized by reacting trimethylalkylammonium iodide with cobalt(II) iodide in acetone. According to X-ray diffraction
data, complexes I and II consist of tetrahedral tetraalkylammonium cations (for I, N-C is 1.481(5)–1.590(8) CNC is 107.3(3)°–111.6(3)°; for II, N-C is 1.485(8)–1.506(10) ? and CNC is 106.9(7)°–111.7(5)°) and [CoI4]2− anions (for I, Co-I is 2.5951(5)–2.6127(5) ? and ICoI is 104.67(2)°–113.23(2)°; for II, Co-I is 2.5914(8)–2.5943(9) ? and ICoI is 107.05(2)°–114.42(5)°). 相似文献
7.
V. V. Sharutin V. S. Senchurin O. K. Sharutina O. A. Fastovets A. P. Pakusina 《Russian Journal of Inorganic Chemistry》2010,55(9):1410-1414
Complexes Ph3(n-Pr)P2+[CoI4]2− (I) and [Ph3(n-Am)P]2+ [CoI4]2− (II) were synthesized by reactions of triphenyl(alkyl)phosphonium iodide with cobalt(II) iodide in acetone. According to the
X-ray diffraction data, complexes I and II consist of tetrahedral triphenyl(alkyl)phosphonium cations (for I, P-C is 1.787(4)–1.804(4) ? and CPC is 106.73(18)°–111.4(18)°; for II P-C is 1.786(6)–1.802(6) ? and CPC is 107.6(3)°–111.7(3)°) and [CoI4]2− anions (Co-I 2.5923(6)–2.6189(6) ?, ICoI 101.86(2)°–113.25(2)° for I; Co-I 2.5899(9)–2.6171(9) 107.01(3)°–110.47(3)° for II). 相似文献
8.
A. Anti?-Jovanovi? M. Kuzmanovi? M. A. Khakoo R. R. Laher 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(13):2363-2367
Measurement of relative band strengths of 10 absorption bands of the E
1Π
u
-X
1Σ
g
+ system of diatomic silver, 107,109Ag2, was performed for the first time. Theoretical analysis of the experimental data, based on Rydberg-Klein-Rees potential energy
curves, revealed that assumption of the r-centroid approximation is valid for this system. Comparison of the measured and computed band strength ratios for 5 pairs
of bands having common lower levels led to the following linear relative electronic transition moment function for the 107,109Ag2
E-X band system: Re ([`(r)]V¢V" ) = 2.36[`(r)]V¢V" - 5.64R_e (\bar r_{V'V'} ) = 2.36\bar r_{V'V'} - 5.64, in arbitrary units, over the 2.65–2.73 ? of internuclear distance. 相似文献
9.
Transitions of the 6υ3 overtone band of 14N2 16O near 775 nm have been studied by continuous-wave cavity ring-down spectroscopy. Line positions and intensities were derived from a fit of the line shape using a hard-collisional profile. The line positions determined with absolute accuracy of 5×10-4 cm-1 allowed us to reveal finer ro-vibrational couplings taking place after J>14 except a strong anharmonic interaction identified by the effective Hamiltonian model. The absolute line intensities have also been retrieved with an estimated accuracy of 2% for a majority of the unblended lines. A new set of ro-vibrational and dipole moment parameters were derived from the experimental values. A comparison between the line positions and intensities of the 6υ3 band obtained in this work and those from previous studies is given. 相似文献
10.
A. D. Smirnov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(6):1026-1030
The vibrational, rotational, and centrifugal constants are calculated for the B
1Π
u
, C
1Π
u
, (1) 1Π
g
, and (2) electronic states of a 85Rb2 molecule. The calculations are based on the semi-empirical potential curves obtained in this work. The results from calculating
the molecular constants are compared with experimental data. The Franck-Condon factors and R
v′v″ centroids are calculated for the electronic transitions B
1Π
u
-X
1Σ
g
+, C
1Π
u
-X
1Σ
g
+, C
1Π
u
-(1) 1Π
g
, and C
1Π
u
-(2) 1Σ
g
+. 相似文献
11.
V. V. Sharutin V. S. Senchurin N. N. Klepikov O. K. Sharutina 《Russian Journal of Inorganic Chemistry》2009,54(2):232-238
Mercury complexes [Ph3AlkP]2+[Hg2I6]2− and [Ph3AlkP]2+[Hg4I10]2− (R = Me, Et, Pr, iso-Pr, Bu, iso-Bu) are synthesized by the reactions of triphenylalkylphosphonium Ph3AlkPI with mercury iodide in acetone with the mole ratio 1: 1 and 1: 2, respectively. According to X-ray diffraction data,
the phosphorus atom in the cations of the [Ph3(iso-Pr)P]2+[Hg2I6]2−, [Ph3BuP]2+[Hg2I6]2−, and [Ph3(iso-Pr)P]2+[Hg4I10]2− complexes has a distorted tetrahedral coordination. The CPC bond angles and P-C bond lengths vary within 107.3(4)°-112.0(4)°
and 1.774(8)-1.827(7) ?. In the [Hg2I6]2− centrosymmetric binuclear anions, the mercury atoms of tetrahedral coordination lie in two near-perpendicular Hg2I6planes. Hg4I4 eight-membered cycles of the [Hg4I10]2− tetranuclear anion are joined into polymeric chains through Hg … I coordination bonds (3.334, 3.681 &OA) due to which Hg
atoms have a trigonal bipyramidal coordination.
Original Russian Text ? V.V. Sharutin, V.S. Senchurin, N.N. Klepikov, O.K. Sharutina, 2009, published in Zhurnal Neorganicheskoi
Khimii, 2009, Vol. 54, No. 2, pp. 267–273. 相似文献
12.
V. V. Sharutin V. S. Senchurin O. A. Fastovets A. P. Pakusina O. K. Sharutina 《Russian Journal of Coordination Chemistry》2008,34(5):367-373
The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony)
hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate
(III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony
chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph4Sb]+ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) ?, respectively. The
coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°,
respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) ?, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°,
the root-mean-square deviation of the atoms from the coordination plane being 0.004 ?.
Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya
Khimiya, 2008, Vol. 34, No. 5, pp. 373–379. 相似文献
13.
In the wavelength range of 231-275 nm, we have studied the mass-resolved dissociation spectra of OCS+ via B2∑+←X2∏3/2(000) and B2∑+←X2∏1/2(000, 001) transitions by preparing OCS+ ions in the well-defined spin-orbit states. The spectroscopic constants ofυ1(CS stretch)=828.9 (810.4) cm-1, υ2(bend)=491.3 cm-1 and υ3(CO stretch)=1887.2 cm-1 for OCS+(B2∑+) are deduced. The observed dependence of the υ2(bend) mode excitation of B2∑+ on the spin-orbit splitting of X2∏(Ω=1/2, 3/2) in the B2∑+←X2∏ transition can be attributed to the K coupling between the (000)2∏1/2 and (010)2∑+1/2 vibronic levels of X2∏ state, which makes the B2∑+(010)←X2∏1/2(000) transition possible. 相似文献
14.
Min Zhao Zhen-xing Li Ting Xie Yao Chang Fu-yan Wu Qin Wang Wen-tao Chen Tao Wang Xing-an Wang Kai-jun Yuan Xue-ming Yang 《化学物理学报(中文版)》2021,34(1):95-101
We study the photodissociation dynamics of CS\begin{document}$_2$\end{document} in the ultraviolet region using the time-sliced velocity map ion imaging technique. The S(\begin{document}$^3$\end{document} P\begin{document}$_J$\end{document} )+CS(\begin{document}$X^1\Sigma^+$\end{document} ) product channels were observed and identified at four wavelengths of 201.36, 203.10, 204.85 and 206.61 nm. In the measured images of S(\begin{document}$^3$\end{document} P\begin{document}$_{J=2, 1, 0}$\end{document} ), the vibrational states of the CS(\begin{document}$X^1\Sigma^+$\end{document} ) co-products were partially resolved and the vibrational state distributions were determined. Moreover, the product total kinetic energy releases and the anisotropic parameters were derived. The relatively small anisotropic parameter values indicate that the S(\begin{document}$^3$\end{document} P\begin{document}$_{J=2, 1, 0}$\end{document} )+CS(\begin{document}$X^1\Sigma^+$\end{document} ) channels are very likely formed via the indirect predissociation process of CS\begin{document}$_2$\end{document} . The study of the S(\begin{document}$^3$\end{document} P\begin{document}$_{J=2, 1, 0}$\end{document} )+CS(\begin{document}$X^1\Sigma^+$\end{document} ) channels, which come from the spin-orbit coupling dissociation process of CS\begin{document}$_2$\end{document} , shows that nonadiabatic process plays a role in the ultraviolet photodissociation of CS\begin{document}$_2$\end{document} .![]()
相似文献
15.
V. V. Sharutin V. S. Senchurin O. K. Sharutina A. P. Pakusina O. A. Fastovets 《Russian Journal of Inorganic Chemistry》2010,55(9):1415-1420
Triphenylbenzylphosphonium tetrachloroaurate (I) and triethanolammonium tetrachloroaurate hydrate (II) were prepared by reacting tetrachloroauric acid in acetone with triphenylbenzylphosphonium and triethanolammonium, respectively.
Triphenylethylphosphonium hexachlorodicuprate (III) was synthesized from triphenylethylphosphonium chloride and copper chloride in acetone. The crystal structures of complexes
I to III were determined by single-crystal X-ray diffraction. The phosphorus atoms in complex I have a nearly undistorted tetrahedral coordination (CPC, 108.3°–110.6°; P-C, 1.788–1.793 ?). The coordination of nitrogen
atoms in the cations of complex II is a distorted tetrahedron (CNC, 111.7°–112.4°). The square coordination of aurum in I and II is only slightly distorted: the ClAuCl angles are 89.6°–90.3° (I) and 89.5°–90.6° (II) and the Au-Cl distances are 2.256–2.278 ? I) and 2.280–2.285 ? (II). The phosphorus atoms in complex III are tetracoordinated (CPC, 106.34°–111.73°; P-C, 1.790–1.795 ?). The copper atoms in III have a distorted tetrahedral coordination (ClCuCl, 98.48°–144.85°; Cu-Cl, 2.1999–2.3263 ?). The central fragment Cu2Cl2 in the anion of complex III is bent relative to the Cu2 axis (the chlorine atom deviates from the Cu2Cl plane by 0.27 ?). 相似文献
17.
V. V. Sharutin I. V. Egorova N. N. Klepikov E. A. Boyarkina O. K. Sharutina 《Russian Journal of Coordination Chemistry》2009,35(3):186-190
The complexes [Ph3BuP]2+[Bi2I8 · 2Me2C=O]2− (II) and [Ph3BuP]2+[Bi2I8 · 2Me2S=O]2− (III) are synthesized by the reactions of triphenyl(n-butyl)phosphonium iodide (I) with bismuth iodide in acetone and dimethyl sulfoxide. In the cations of complexes I–III, the P atoms have a distorted tetrahedral coordination (CPC angles 106.3(2)°–112.0(3)°). The butyl group in cation I is disordered over two positions. In the binuclear centrosymmetric anions of structures II and III, the octahedrally coordinated bismuth atoms are linked in pairs by two bridging (br) iodine atoms (Bi-Ibr 3.1508(7) and 3.2824(8) ? in compound II, 3.1961(3) and 3.3108(3) ? in complex III), which are coplanar to four terminal (t) iodine atoms (Bi-It 2.9260(7) and 2.9953(6) ? in complex II, 2.9206(3) and 2.9786(3) ? in complex III). The two remaining positions at the bismuth atom are occupied by the iodine atom (Bi-It 2.8531(7) ? in complex II, 2.8984(3) ? in complex III) and O atom of the organic molecule (Bi-O 2.747(6) ? in complex II, 2.507(3) ? in complex III).
Original Russian Text ? V.V. Sharutin, I.V. Egorova, N.N. Klepikov, E.A. Boyarkina, O.K. Sharutina, 2009, published in Koordinatsionnaya
Khimiya, 2009, Vol. 35, No. 3, pp. 188–192. 相似文献
18.
IR and single-crystal X-ray diffraction study are carried out for compound, C36H112Cl9Fe3N18O8P6(I). It crystallizes in the orthorhombic space group P212121 with a = 14.2992(3), b = 21.4351(4), c = 25.5407(5) ?, V = 7828.3(3) ?3, ρcalcd = 1.553 g/cm3, Z = 4. The FeCl fragment is coordinated with chlorine atom of two water molecules and three HMPA molecules to form a cation,
with a distorted octahedral coordinate geometry. In the crystal I, the cation is linked with HMPA by the O-H…O hydrogen bond.
The chiral crystal is formed through self-assembly even from achiral molecules. 相似文献
19.
Oscillations in the concentration of intermediates were obtained when a model without reaction IO
3
–
+I–+2H+HIO+HIO2 was used for the simulation of the Bray-Liebhafsky process. 相似文献
20.
以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃. 相似文献