Coupled cluster calculations for the interstellar molecule HC3NH+

An accurate equilibrium structure has been established for the linear interstellar molecular cation HC₃NH⁺: r _1e(CH) = 1.0703Å, R _1e(C₍₁₎C₍₂₎) = 1.2097 Å, R _2e(C₍₂₎C₍₃₎) = 1.3509Å, R _3e(C₍₃₎N) = 1.1448 Å and r _2e(NH) = 1.0079Å. Ground-state rotational constants for less abundant isotopomers are predicted with an uncertainty of about 0.02 MHz. The equilibrium dipole moment of HC₃NH⁺ is calculated to be 1.61 D.     

The rotational levels of the ground vibrational state of formaldehyde

A variational procedure for rovibrational energy levels and wavefunctions of centrally connected tetra-atomic molecules is extended to include high rotational states, and in particular, J ? 10 levels for the vibrational ground state of formaldehyde. It is very important to do this because it has made possible the calculation of the usual rotational spectroscopic constants which correspond to the forcefield and geometry. A direct comparison with the ‘observed’ spectroscopic constants is therefore possible. The geometry and forcefield are refined against 65 J = 0 levels of H₂CO, 6 J = 0 levels of D₂CO, 42 J = 1, 70 J = 2 and 98 J = 3 levels of the ground and fundamentals of H₂CO and D₂CO, using an iterative scheme. The mean absolute error of the J = 0 levels is 1·10 cm^?1 and that for J ≠ 0 is 0·005 cm^?1, and the predicted geometry is CH = 1·10064 Å, CO = 1·20296 Å and HCO = 121·648°. Finally, the rotational constants A, B, and C for the ground state are 281956, 38846 and 34003 MHz, compared with the observed values 281971, 38836, and 34002 MHz. The centrifugal distortion constants Δ_J , Δ_JK , Δ_K and δ_J , are 77, 1275, 18113 and 11 kHz compared with 75, 1291, 19422 and 10 kHz. These results underline the accuracy of the new quartic forcefield.     

Stereochemical studies of oligomers XXIX. Reinvestigation of the structure of N-m-tolyl phthalimide

C₁₅H₁₁NO₂, Mr 237.3, monoclinic, space groupC _c, a=8.539(2),b=19.865(4),c=7.599(2)?,β=111.44(2)°,V=1199.8 ?³,Z=4,D _c=1.31 gcm⁻³,λ(CuKα)=1.5418 ?,μ=6.74cm⁻¹,F(000)=496, room temperature. The structure was solved by direct methods with SHELX-86 and refined down to agreement valueR=0.046 for 1117 reflections above 2σ(I). The angle between the plane of the phthalimide group, which shows a little bent [1.2(2)°] between its two rings, and the tolyl group is 56.1(1)°. The packing of the molecules is stabilized by van der Waal’s forces only. Part XXVIII: Bocelli and Rizzoli (1990)     

Ab initio calculations for propyne and the hydrogen bonded complex NH H C C CH 3 3

The hydrogen-bonded cluster NH₃ …H—C≡C—CH₃ has been investigated by means of the coupled electron pair approximation, making use of a basis set of 198 contracted Gaussian-type orbitals. The calculated equilibrium structure is r _1^e (N—H) = 1?0127 Å, α_e(∠HN…H) = 112?32°, R _1^e (N…H) = 2?3593 Å, r _2^e (acetylenic C—H) = 1?0690 Å, R _2^e (C≡C) = 1?2078 Å, R _3^e (C—C) = 1?4711 Å, r _3^e (C—H) = 1?0894 Å and β_e(∠CCH) = 110?50°. The recommended equilibrium dissociation energy is D _e = 12?4±0?5 kJ mol^-1 and the calculated equilibrium dipole moment is μ_e = – 1?468 D, with the positive end of the dipole at the ammonia protons. Harmonic wavenumbers and absolute infrared intensities for the totally symmetric modes are calculated. Compared with free propyne the acetylenic CH stretching vibration experiences a bathochromic shift of 93 cm^-1 and an intensity enhancement by a factor of 5?5.     

Experimental determination of the potential energy curves of the I(3/2u) and I(3/2g) states of Kr+ 2

The I(3/2u) and I(3/2g) states of Kr⁺ ₂ have been investigated by pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy following (2 + 1′) resonance-enhanced multiphoton excitation via the 0⁺ _g Rydberg state located below the Kr?([4p]⁵5p[1/2]₀) + Kr(¹S₀) dissociation limit of Kr₂. From the positions of a large number of vibrational bands in the spectra of the ⁸⁴Kr₂ and ⁸⁴Kr-⁸⁶Kr isotopomers, the adiabatic ionization potentials (IP(I(3/2u)) = 112672.4 ± 0.8cm^?1, IP(I(3/2g)) = 111 395.0 ± 1.4cm^?1), the dissociation energies (D ⁺ ₀(I(3/2u)) = 368.8 ± 2.0cm^?1, D ⁺ ₀(I(3/2g)) = 1646.2 ± 2.3cm^?1) and vibrational constants for both ionic states have been determined. Potential energy curves have been extracted which perfectly reproduce all experimental observations and are accurate over a wide range of energies and internuclear distances. The equilibrium internuclear distances (R ⁺ _e(I(3/2u)) = 4.11 ± 0.04 Å, R ⁺ _e(I(3/2g)) = 3.35 ± 0.10 Å) have been derived by comparing the intensity distribution in the PFI-ZEKE photoelectron spectra to calculated Franck-Condon factors. The dissociation energy of the I(3/2g) state and the equilibrium internuclear distance of the I(3/2u) state differ markedly from previously reported values.     

The vibrational numbering and improved constants of the A3Π1u state of I2

The A-X system of I₂ has been recorded in absorption, under conditions of medium resolution, over the region 8000 – 13 400 Å. Bandheads in progressions based on v″ = 6 through 18 have been measured and assigned. A new vibrational numbering for the A state is proposed, which leads to more reliable values for the important constants of the A state: T_e = 10 906 ± 3 cm^?1, D_e = 1641 ± 3 cm^?1, ω_e = 92.5 ± 0.5 cm^?1, ω_ex_e = 1.20 ± 0.08 cm^?1, ω_ey_e = ?0.062 ± 0.006 cm^?1.     

The 2880-Å emission spectrum of I2: Ion-pair states near 47 000 cm−1

An emission system of I₂ in Ar in the region 2830–2890 Å is examined under high resolution and found to display fine violet-degraded band structure. This system is interpreted as a charge-transfer transition originating from an ion-pair state near 47 000 cm^?1 and terminating on a weakly bound state which dissociates to two ground-state atoms. This interpretation is supported by spectral simulations employing a bound-free model. The transition is tentatively assigned as $\text{0}{}_{\mathrm{<mtext>g</mtext>}}{}^{\mathrm{?}}\text{→ 2431 0}{}_{\mathrm{<mtext>u</mtext>}}{}^{\mathrm{?}}\text{(}{}^3\text{Π}\text{)}$, according to which the excited state becomes the fourth ion-pair state near 47 000 cm^?1 to be experimentally characterized, and the lower state is the last component of the lowest ³Π state to be identified. The vibrational assignments include about 45 bands in ¹²⁷I₂ and ¹²⁹I₂, spanning v′ = 0–4 and v″ = 6–19, but with the numbering of the lower state remaining uncertain by several units. The main spectroscopic constants for the excited state are T_e = 47 070 cm^?1, ?_e = 105.7 cm^?1, ?_ex_e = 0.49 cm^?1. The spectral simulations place the lower state's potential curve 34 650 cm^?1 below the upper state at R = R′_e, with slope ?850 cm^?1/Å. For our “best” numbering of the lower state, ?_e = 20.5 cm^?1, ?_ex_e = 0.29 cm^?1, T_e = 12 190 cm^?1, and D_e = 360 cm^?1.     

Structure of Quinoline-4-Carboxaldehyde-2,4-Dinitrophenyl-N Methylhydrazone

Abstract

The crystal structure of the title compound, C₁₇H₁₃N₅O₄, has been determined by single crystal x-ray diffraction at room temperature. The molecule is not planar, with dihedral angles of 7.2(1)° between the quinoline ring and N-methylhydrazone group, and 17.45(2)° between the N-methylhydrazone group and the phenyl ring. The crystal parameters of this compound are as follows: monoclinic P 21/n, a=9.525(2)Å, b = 15.192(2) Å, c = 11.302(2) A, β = 94.722(3)°, V = 1629.8(6) ų, Z = 4, Dx = 1.432 g/cm³, F(000) = 728, λ (MoKα) = 0.71070 Å, μ = 0.106 mm^?1, R_int = 0.017. The structure was solved by SHELXS-86 and refined by SHELXL-93. R = 0.07 for 2438 observed reflections with I > 2σ (I).     

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states of the C₂Br radical, correlating at linear geometries with ²Σ⁺ and ²Π states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, RCC=1.2621Å, R _CBr=1.7967Å, ∠ CCBr=156.1°, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C₂F and C₂Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Σ ,Π_1/2,Π_3/2 vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5 K have been calculated for the ¹² C¹² C⁷⁹Br isotopomer, to an upper limit of 2000 cm^?1, using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.     

Structure of 4,4′-butane-(1,4,7-three-p-tolylsulphonyl-1,4,7-three amine) diphthalonitrile

Abstract

The crystal structure of the title compound, C₄₁ H₃₅ N₇ O₆ S₃ was determined as monoclinic by single crystal X-Ray diffraction technique. The molecular structure was identified by IR, ¹H-NMR, ¹³C-NMR and elemental analysis. The crystal parameters of this compound are as follows: monoclinic P 2 1/n, a = 12.694(2) Å, b = 26.204(2) Å, c = 13.005(2) Å, β = 102.95(2)°, V = 4216.02(1) Å.³, Z = 4, Dx = 1.289 g/cm³, F(000) = 1704, λ (MoKα) = 0.71070 Å, μ = 0.2 mm^?1. The structure was solved by SHELXS-97 and refined by SHELXL-97. R = 0.06 for 3178 observed reflections with I > 2σ (I).     

Intensities and half-widths at different temperatures for the 201III←000 band of CO2 at 4854 cm−1

Measurements made at temperatures of 197, 233, and 294°K of the absolute intensities and self-broadening coefficients for the vibration-rotation lines of the 201_III←000 band of the ¹²C¹⁶O₂ molecule, are reported. From these measurements, values have been derived for the vibration-rotation interaction factor (F_VR), the purely vibrational transition moment (|R(O)|), and the intensity (S_Band). The results are: E_VR(m) = 1+(2.2±0.7)×10^?3m+(5.6±1.6)×10^×5m², |R(0)| = (2.064±0.017)×10^?3 debye, S_Band = 21,329±69 cm^?1km^?1atm^?1_STP. The results for the self-broadening coefficients are presented in the text.     

Infrared bands of 12C2HD

The rotational structure of about 40 bands of ¹²C₂HD observed in the region 6000?600 cm^?1 has been measured and interpreted with the purpose of determining a comprehensive set of molecular constants for this isotopic variety of acetylene. Combining these data with the results for ¹²C₂H₂ and ¹²C₂D₂, a reevaluation of the equilibrium internuclear distances for the acetylene molecule has been made: $\text{r}{}_{\mathrm{e}}\text{(CH) = 1.06215 ± 17 × 10}{}^{\mathrm{?5}}\text{A}\text{?}$ and $\text{r}{}_{\mathrm{e}}\text{(CC) = 1.20257 ± 9 × 10}{}^{\mathrm{?5}}\text{A}\text{?}$ were obtained. This paper presents all the molecular constants derived in this study.     

Noble gas halides: The B → X and D → X systems of 136Xe35Cl

The B → X (2870–3100 Å) and D → X (2250–2370 Å) band systems of ¹³⁶Xe³⁵Cl are photographed and vibrationally analyzed. A simultaneous least-squares fit of 41 band-heads in the B-X system and 35 in D-X yields, in part, the following constants (in cm^?1): T_eB = 32 405.8, T_eD = 42 347.9, ω_eB = 194.75, ω_eD = 204.34, ω_eX = 26.22. The ground state dissociation energy ($\text{D}$″_e) is estimated to be 281 ± 10 cm^?1. Potential curves are derived for all three states through Franck-Condon calculations. From these curves the D-state internuclear distance is 0.09 ± .02 Å smaller than the B-state distance.     

Gas‐phase reactions of Cl atoms with hydrochloroethers: relative rate constants and their correlation with substituents' electronegativities

Rate constants for the reactions of Cl atoms with CH₃OCHCl₂ and CH₃OCH₂CH₂Cl were determined at (296 ± 2) K and atmospheric pressure using synthetic air as bath gas. Decay rates of these organic compounds were measured relative to the following reference compounds: CH₂ClCH₂Cl and n‐C₅H₁₂. Using rate constants of 1.33 × 10^?12 and 2.52 × 10^?10 cm³ molecule^?1 sec^?1 for the reaction of Cl atoms with CH₂ClCH₂Cl and n‐C₅H₁₂, respectively, the following rate coefficients were derived: k(Cl + CH₃OCHCl₂) = (1.05 ± 0.11) × 10^?12 and k(Cl + CH₃OCH₂CH₂Cl) = (1.14 ± 0.10) × 10^?10, in units of cm³ molecule^?1 s^?1. The rate constants obtained were compared with previous literature data and a correlation was found between the rate coefficients of some CH₃OCHR¹R² + Cl reactions and ΔElectronegativity of ? CHR¹R². Copyright © 2008 John Wiley & Sons, Ltd.     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法，分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组，对BH₂和AlH₂分子的结构进行了优化计算，得到BH₂分子的稳态结构为C_2v构型，电子态为²A₁、平衡核间距R_BH=0.1187nm、键角∠HBH=128.791°、离解能D_e=3.65eV、基态振动频率ν₁(a₁)=1020.103cm^-1,ν₂(a₁)=2598.144cm^-1,ν₃(b₂)=2759.304cm^-1.AlH₂分子的稳态结构也为C_2v构型，电子态为²A₁、平衡核间距R_AlH=0.1592nm、键角∠HAlH=118.095°、离解能D_e=2.27eV、基态振动频率ν₁(a₁)=780.81cm^-1,ν₂(a₁)=1880.81cm^-1，ν₃(b₂)=1910.46cm^-1.采用多体项展式理论推导了基态BH₂和AlH₂分子的解析势能函数，其等值势能图准确再现了BH₂和AlH₂分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH₂反应中存在鞍点，活化能为150.204kJ/mol；AlH+H→AlH₂反应中也存在鞍点，活化能为54.8064kJ/mol. 关键词： 2')" href="#">BH₂ 2')" href="#">AlH₂ Murrell-Sorbie函数 多体项展式理论 解析势能函数     

The intermolecular potential of NH+ 4-Ar I. Calculations for the internal rotor structure of the v 3 band

The intermolecular potential energy surface of the electronic ground state of the ammonium-argon ionic dimer, NH⁺ ₄-Ar, is calculated by ab initio methods using different levels of theory (MP2, MP4) and basis sets (aug-cc-pVXZ, X = D/T/Q). The deformation of the ammonium ion in the complex is shown to be small and its geometry is therefore fixed in these calculations to the tetrahedral structure optimized for the bare ion. The global minimum of the potential corresponds to a proton-bound structure with C_3v symmetry (R_e ≈ 3.4 Å, D_e ≈ 950 cm^?1) and the barrier to internal rotation between the four equivalent minima is around 200 cm^?1. The three-dimensional potential is expanded in tetrahedral harmonics whose radially dependent coefficients, V_i (R), are compared for the considered levels of theory. The rotation-intermolecular vibration Hamiltonian is solved using a two-dimensional fixed-R representation of the calculated potentials, V_i , ≡ V_i (R ^eff), where the effective intermolecular separation, RR^eff, is determined from the experimental rotational constants of the complex. The accuracy of these parametrized potential energy surfaces is judged by their ability to reproduce the hindered rotor subband structure in the experimental v ₃(t ₂) infrared band of the complex. The simulations using the potentials calculated at the MP2/aug-cc-pVTZ or higher levels of theory reproduce the coarse structure of the experimental spectrum well. Further improvement could be achieved by least-squares fitting the potential parameters to the observed subband positions. The fitted V ₃ and V ₄ parameters remain in close agreement with those determined from the ab initio calculations but the anisotropy of the potential is significantly different from that in a previous least-squares fit of V ₃ alone.     

Line strength and collisional broadening coefficients of H2O at 2.7 μm for natural gas quality assurance applications

We employed tunable diode laser absorption spectroscopy to measure the line strength, the methane (CH₄), ethane (C₂H₆) and the propane (C₃H₈) broadening coefficients for the 523–422 H₂O transition at 3619.61 cm^?1. Water amount fractions generated by a stable and accurate humidity transfer standard, traceable to the SI units via the German national humidity standard, were used to calibrate the spectroscopic line strength measurements. We focus on the traceability of the measured line data to the SI and on uncertainty assessments following the guidelines of the Guide to the Expression of Uncertainty in Measurement. We determined the line strength to be (8.42 ± 0.07)×10^?20 cm^?1/(cm^?2 molecule) corresponding to a relative uncertainty of ±0.8%. To the best of our knowledge, we report the first methane, ethane and propane broadening coefficients of (8.037 ± 0.056)×10^?5 cm^?1/hPa, (9.077 ± 0.064)×10^?5 cm^?1/hPa and (10.469 ± 0.073)×10^?5 cm^?1/hPa for the 523–422 H₂O transition at 3619.61 cm^?1, respectively. The relative combined uncertainties of the stated CH₄, C₂H₆ and C₃H₈ broadening coefficients are in the ±0.7% range.     

I. Electron-impact ionization and dissociation of C<Subscript>2</Subscript>H<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and C<Subscript>2</Subscript>D<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections for electron-impact ionization and dissociation of C₂H₂⁺ and C₂D₂⁺ have been measured for electron energies ranging from the corresponding thresholds up to 2.5 keV. The animated crossed beams experiment has been used. Light as well as heavy fragment ions that are produced from the ionization and the dissociation of the target have been detected for the first time. The maximum of the cross-section for single ionization is found to be (5.56 ± 0.03)× 10^-17 cm² around 140 eV. Cross-sections for dissociation of C₂ H₂⁺ (C₂D₂⁺) to ionic products are seen to decrease for two orders of magnitude, from C₂D⁺ (12.6 ± 0.3) × 10^-17 cm² over CH⁺(9.55 ± 0.06) × 10^-17 cm², C⁺ (6.66 ± 0.05) × 10^-17 cm², C₂⁺ (5.36 ± 0.27) × 10^-17 cm², H⁺ (4.73 ± 0.29) × 10^-17 cm² and CH₂⁺ (4.56 ± 0.27) × 10^-18 cm² to H₂⁺ (5.68 ± 0.49) × 10^-19 cm². Absolute cross-sections and threshold energies have been compared with the scarce data available in the literature.     

A monte-carlo/molecular dynamics study of the diffusional recombination kinetics of C(a) + O(a) → CO(g) on Pt(111)

The diffusion constants for C and O adsorbates on Pt(111) surfaces have been calculated with Monte-Carlo/Molecular Dynamics techniques. The diffusion constants are determined to be D_C(T)=(3.4 × 10^?3e^{$\text{?13156}\text{T}$})cm²s^?1 for carbon and D_O(T) = (1.5×10^?3 e^{$\text{?9089}\text{T}$}) cm² s^?1 for oxygen. Using a recently developed diffusion model for surface recombination kinetics an approximate upper bound to the recombination rate constant of C and O on Pt(111) to produce CO_(g) is found to be (9.4×10^?3 e^{$\text{?9089}\text{T}$}) cm² s^?1.     

A precise solution of the rotation bending Schrödinger equation for a triatomic molecule with application to the water molecule

In this paper we report the results of improving the non-rigid bender formulation of the rotation-vibration Hamiltonian of a triatomic molecule [see A. R. Hoy and P. R. Bunker, J. Mol. Spectrosc., 52, 439 (1974)]. This improved Hamiltonian can be diagonalized as before by a combination of numerical integration and matrix diagonalization and it yields rotation-bending energies to high values of the rotational quantum numbers. We have calculated all the rotational energy levels up to J = 10 for the (v₁, v₂, v₃) states (0, 0, 0) and (0, 1, 0) for both H₂O and D₂O. By least squares fitting to the observations varying seven parameters we have refined the equilibrium structure and force field of the water molecule and have obtained a fit to the 375 experimental energies used with a root mean square deviation of 0.05 cm^?1. The equilibrium bond angle and bond length are determined to be 104.48° and 0.9578 Å respectively. We have also calculated these energy levels using the ab initio equilibrium geometry and force constants of Rosenberg, Ermler and Shavitt [J. Chem. Phys., 65, 4072 (1976)] and this is then the first complete ab initio calculation of rotation-vibration energy levels of high J in a polyatomic molecule to this precision. the rms fit of these ab initio energies to the experimental energies for the H₂O molecule is 2.65 cm^?1.