The microwave spectrum,harmonic force field,and structure of difluorodichloromethane

Very large numbers of rotational transitions have been accurately measured for ¹²CF₂³⁵Cl₂, ¹²CF₂³⁵Cl³⁷Cl, and ¹³CF₂³⁵Cl₂, and have been analyzed for rotational constants and quartic centrifugal distortion constants. The distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work), and with ab initio force constants also evaluated in the present work, to give an approximate harmonic force field. The rotational constants and force field have been used to evaluate ground state effective, substitution, and ground state average structures for the molecule.     

Anharmonic force fields of cis- and trans-S1 C2H2

We calculate second-order vibrational perturbation theory (VPT2) anharmonic force fields for the cis and trans conformers of S₁ C₂H₂, and compare the results to experiment. The vibrational assignments of recently observed levels belonging to the cis well are of particular interest. A refined estimate of the cis origin position (44,870?±?10?cm^?1) is proposed, and preliminary low-energy fits to the global J?=?K?=?0 trans level structure are also described. The performance of perturbation theory in this isomerizing system is examined, and both surprising successes and failures are encountered. We examine these and their causes, and offer practical suggestions for avoiding the pitfalls of applying perturbation theory to systems with large amplitude motions.     

Anharmonic force field for methanol

An ab initio quartic anharmonic force field for methanol has been calculated at the equilibrium position using the CCSD(T) method for the structure and the harmonic potential energy surface, and the MP4(SDQ) method for the anharmonic part of the surface. A triple zeta basis set was employed with symmetrized curvilinear internal valence coordinates in all calculations. The internal coordinate force field constants have been transformed into force constants in the dimensionless normal coordinate representation for various isotopomers. Vibrational term values for CH₃OH, CH₃OD, CD₃OH, and CD₃OD have been obtained using second order perturbation theory. Particular care has been devoted to the inclusion of Fermi resonance interactions between different vibrational states. A good accuracy has been achieved in the calculation of the fundamentals for all the isotopomers, the mean absolute error being 5.8 cm^?1.     

The anharmonic force field of cis-1-chloro-2-fluoroethylene

A comprehensive anharmonic vibrational analysis of cis-1-chloro-2-fluoroethylene and its isotopomers has been performed on the basis of a complete ab initio quartic force field constructed by means of second-order Møller-Plesset perturbation theory (MP2) and the coupled-cluster singles and doubles approach, augmented for structural optimization and harmonic force field by a contribution of connected triple excitations (CCSD(T)). The theoretical force field was scaled by global least-squares fitting to all spectroscopic data and parameters experimentally determined for this molecule. This final force field, employing standard perturbation theory, yields a complete set of spectroscopic molecular constants providing a critical assessment of experimental rotational and centrifugal distortion constants, fundamentals, overtones, and combination bands determined over many years. Effects of Fermi and Darling-Dennison resonances were included by matrix diagonalization.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

Nuclear quadrupole coupling in chloroform and calibration of ab initio calculations

The complex hyperfine structures in the J = 1 ← 0, and J = 2 ← 1 ground state rotational transitions of ³⁵Cl₃CH and ³⁵Cl₂³⁷ClCH were resolved and measured at conditions of supersonic expansion. Accurate spectroscopic constants for the two isotopomers have been derived from global fits of the hyperfine structure together with hyperfine-free high-J millimetre wave data. The complete inertial and principal quadrupole tensors of the chlorine nuclei have been determined, and the symmetric top treatment for ³⁵Cl₃CH and the asymmetric top treatment for ³⁵Cl₂³⁷ClCH yield identical results for the principal tensor components of the ³⁵Cl nucleus. The availability of precise experimental splitting constants for many molecules allows benchmarking of ab initio field gradient calculations, and it is found that for the chlorine nucleus optimum predictive performance for molecules of moderate size is obtained at the B3LYP/aug-cc-pVDZ level by using a scaling factor of 1.0619(23).     

Theoretical investigations of spectroscopic parameters and molecular constants for electronic ground state of Cl2 and its isotopes

The potential energy curve of the Cl 2(X1Σg+) is investigated by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in combination with the largest correlation-consistent basis set, aug-cc-pV6Z, in the valence range. The theoretical spectroscopic parameters and the molecular constants of three isotopes, 35Cl2, 35Cl37Cl and 37Cl2, are studied. For the 35Cl2 (X1Σg+), the values of D0 , De , Re , ωe , ωeχe , αe and Be are obtained to be 2.3921 eV, 2.4264 eV, 0.19939 nm, 555.13 cm-1 , 2.6772 cm-1 , 0.001481 cm-1 and 0.24225 cm-1 , respectively. For the 35Cl37Cl(X1Σg+), the values of D0 , De , Re , ωe , ωeχe , αe and Be are calculated to be 2.3918 eV, 2.4257 eV, 0.19939 nm, 547.68 cm-1 , 2.6234 cm-1 , 0.00140 cm-1 and 0.23572 cm-1 , respectively. And for the 37C2 (X1Σg+), the values of D0 , De , Re , ωe , ωeχe , αe and Be are obtained to be 2.3923 eV, 2.4257 eV, 0.19939 nm, 540.06 cm-1 , 2.5556 cm-1 , 0.00139 cm-1 and 0.22919 cm-1 , respectively. These spectroscopic results are in good agreement with the available experimental data. With the potential of Cl2 molecule determined at the MRCI/aug-cc-pV6Z level of theory, the total of 59 vibrational states is predicted for each isotope when the rotational quantum number J equals zero (J = 0). The theoretical vibrational levels, classical turning points, inertial rotation and centrifugal distortion constants are determined when J = 0, which are in excellent accordance with the available experimental findings.     

Structure and thermodynamic properties of positive and negative cluster ions in saturated vapour over barium dichloride

Geometrical structure, vibration spectra, and enthalpies of dissociation have been investigated for the ions BaCl₃^?, Ba₂Cl₃⁺, Ba₃Cl₅⁺, and Ba₄Cl₇⁺ which were detected earlier in the saturated vapour over BaCl₂. Quantum chemical methods of density functional theory, the second and the fourth order Møller–Plesset perturbation theory have been applied. The effective core potential with cc-pVTZ basis set for barium atom and two full-electron basis sets including the diffuse and polarised basis functions for chlorine atom were used. The effect of the basis set size and the computation method on the results was analysed. According to the results, all the ions possess the compact shaped structure. The equilibrium geometrical structures were found as follows: the planar D_3h for BaCl₃^?, triple bridged bipyramidal D_3h for Ba₂Cl₃⁺, hexabridged D_3h for Ba₃Cl₅⁺, and septuple bridged C_2v for Ba₄Cl₇⁺. For positive ions, the different isomeric structures were considered, but no isomers for these ions have been found. The geometrical parameters and vibration frequencies were utilised for computing of thermodynamic functions of the ions, and then the thermodynamic functions were used for the treatment of the experimental mass spectrometric data. The enthalpies of formation Δ_fH°(0 K) of the ions were determined (in kJ/mol): ?994 ± 6 (BaCl₃^?), ?481 ± 10 (Ba₂Cl₃⁺), ?1276 ± 14 (Ba₃Cl₅⁺), ?2048 ± 35 (Ba₄Cl₇⁺).     

Spectra and structure of organogermanes: Microwave and Raman spectra of methyltrichlorogermane

The microwave spectrum of methyltrichlorogermane has been investigated in the region 26.5 to 40.0 GHz. The ground state rotational constants, B, were found to be 1602.19, 1601.42, 1601.10, 1600.71, 1600.02, 1537.84, 1537.10, and 1536.36 MHz for the symmetric top molecules CH₃⁷⁰Ge³⁵Cl₃, CH₃⁷²Ge³⁵Cl₃, CH₃⁷³Ge³⁵Cl₃, CH₃⁷⁴Ge³⁵Cl₃, CH₃⁷⁶Ge³⁵Cl₃, CH₃⁷⁰Ge³⁷Cl₃, CH₃⁷²Ge³⁷Cl₃, and CH₃⁷⁴Ge³⁷Cl₃, respectively. For the asymmetric top molecules CH₃⁷²Ge³⁵Cl₂³⁷Cl and CH₃⁷⁴Ge³⁵Cl₂³⁷Cl the ground state rotational constants A, B, and C were found to be 1597.96, 1559.31, 1203 and 1597.17, 1558.59, 1207 MHz, respectively. From the rotational constants the r_s values for the GeCl bond distance of 2.135 ± 0.006 Å and the CGeCl bond angle of 106.0 ± 0.7° were obtained. The centrifugal distortion constant for the CH₃Ge³⁵Cl₃ species was calculated to be 0.35 ± 0.08 kHz. The Raman spectra of methyltrichlorogermane has been recorded in the gas phase and the methyl torsional overtone (Δν = 2) was observed. From the observed frequency shift the barrier to internal rotation has been calculated to be 1.45 kcal/mole.     

Force constant calculations of NCl3 and PCl3

A method based on the least-squares fitting of the observed vibrational frequencies, centrifugal distortion constants, mean-square amplitudes, and vibration-rotation interaction constants with respect to the harmonic force constants has been employed to determine the harmonic force field of NCl₃ and PCl₃. The results are compared with those obtained by other authors. An improved structure of PCl₃ has also been determined by analysis of the microwave spectrum of the P³⁷Cl₃ and P³⁵Cl₂³⁷Cl isotopic species. Two structures have been obtained with the following values of the parameters

$\text{r}{}_{\mathrm{s}}\text{(PCl)=2.0450±0.0072}\text{A}\text{?}\text{Cl}\text{P}\text{Cl=100°12′±20′}$

$\text{r}{}_{\mathrm{s}}\text{(PCl)=2.0426±0.0005}\text{A}\text{?}\text{Cl}\text{P}\text{Cl=100°6′±1′}$

     

Force constant analysis of molecular groups in apatite solids

The results of normal coordinte analyses demonstrate that the simple Urey-Bradley force field gives a reasonable representation of the potential-energy function of PO₄^3? in pyromorphite (Pb₁₀(PO₄)₆Cl₂) but is unsatisfactory for AsO₄^3? and VO₄^3? in mimetite (Pb₁₀(AsO₄)₆Cl₂) and vanadinite (Pb₁₀(VO₄)₆Cl₂). respectively. Theoretical band assignments are made for PO₄^3? in pyromorphite using simple Urey-Bradley force field and based on a good frequency fit, a physically reasonable set of molecular force constants and some experimental confirmation. The general order of magnitude and trends in force constants are physically realistic. The theoretical analysis provides additional confirmation for the assignment of the v₂ bending mode to a higher-frequency, lower-intensity band at 436 cm^?1 in the infrared. Eigenvector calculations allow determination of which internal coordinates are major contributors to the various normal modes.     

The quadratic potential function and average structure of sulphur dichloride,SCl2, from its microwave spectrum

The microwave spectra of ³²S³⁵Cl₂ in the ground (000) and v₂ = 1 excited vibrational (010) states, and of ³²S³⁵Cl³⁷Cl in the (000) state, have been measured. Values of the quadratic potential constants have been determined from the centrifugal distortion constants and the variation of the inertial defect with vibrational state. A partial substitution structure has been evaluated. The potential function has been used to obtain average structures of ³²S³⁵Cl₂ in the (000) and (010) states. The frequencies of the three fundamental vibrations of ³²S³⁵Cl₂ have been predicted, and agree extremely well with observed values. A comparison is made of the bonding in SCl₂ and related molecules.     

The millimeter wave spectrum of phosphorus oxychloride

Millimeter wave rotational spectra of phosphorus oxychloride (OPCl₃) in the ground and excited vibrational states have been recorded and analyzed. The v₅ = 1 and v₆ = 1 state spectra show large splittings due to l resonance and the effect of the 2, -1 term r_t. Coriolis constants have been obtained for the two lowest degenerate states. The spectra of the asymmetric top species OP³⁵Cl₂³⁷Cl have been analyzed and centrifugal distortion constants obtained. These have been used to determine the harmonic force field of the molecule.     

High-resolution analysis of the ν1 and ν5 bands of phosgene 35Cl2CO and 35Cl37ClCO

Fourier transform spectra of phosgene (Cl₂CO) have been recorded in the 11.75 and 5.47 μm spectral regions using a Bruker IFS125HR spectrometer at resolutions of 0.00102 and 0.0015 cm^?1, respectively, leading to the observation of the ν₅ and ν₁ vibrational bands of the two isotopologues ³⁵Cl₂CO and ³⁵Cl³⁷ClCO. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians and/or a Hamiltonian matrix accounting for resonance effects when necessary. In this way, it was possible to reproduce the upper state ro-vibrational levels to within the experimental accuracy, i.e. ～0.17 × 10^?3 cm^?1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band centres: ν₀(ν_5, ³⁵Cl₂CO) = 851.012737(20) cm^?1, ν₀(ν_5, ³⁵Cl³⁷ClCO) = 849.995451(90) cm^?1, ν₀(ν_{2 +} ν_3, ³⁵Cl³⁷ClCO) = 864.42370(50) cm^?1, ν₀(ν_1, ³⁵Cl₂CO) = 1828.202514(40) cm^?1 and ν₀(ν_1, ³⁵Cl³⁷ClCO) = 1827.246444(20) cm^?1.     

The analytical potential energy function of flue gas SO2（X1A1）

The equilibrium structure of flue gas SO2 is optimized using the density functional theory （DFT）/B3P86 method and CC-PV5Z basis. The result shows that it has a bent （C2v, X1A1） ground state structure with an angle of 119.1184°. The vibronic frequencies and the force constants are also calculated. Based on the principles of atomic and molecular reaction statics （AMIIS）, the possible electronic states and reasonable dissociation limits for the ground state of SO2 molecule are determined. The potential functions of SO and 02 are fitted by the modified Murrell-Sorbie＋c6 （M-S＋c6） potential function and the fitted parameters, the force constants and the spectroscopic constants are obtained, which are all close to the experimental values. The analytic potential energy function of the SO2 （X1A1） molecule is derived using the many-body expansion theory. The contour liues are constructed, which show the static properties of SO2 （XIA1）, such as the equilibrium structure, the lowest energies, the most possible reaction channel, etc.     

First far-infrared high-resolution analysis of the ν2 and ν4 bands of phosgene 35Cl2CO and 35Cl37ClCO

ABSTRACT

A Fourier transform spectrum of phosgene (Cl₂CO) has been recorded in the 17.3-μm spectral region at a temperature of 180 K and at a resolution of 0.00102 cm^?1 using a Bruker IFS125HR spectrometer coupled to synchrotron radiation, leading to the observation of the ν₂ and ν₄ vibrational bands of the two isotopologues ³⁵Cl₂CO and ³⁵Cl³⁷ClCO. The corresponding upper-state ro-vibrational levels were fit using a Hamiltonian model accounting for the A-type Coriolis interaction linking the rotational levels of the 2¹ and 4¹ vibrational states. In this way, it was possible to reproduce the upper-state ro-vibrational levels to within the experimental uncertainty, i.e. ～0.30 × 10^?3 cm^?1. Very accurate rotational and centrifugal distortion and interaction constants were derived from the fit, together with the following band centres: ν₀(ν_2, ³⁵Cl₂CO) = 572.526299(30) cm^?1, ν₀(ν_4, ³⁵Cl₂CO) = 582.089026(30) cm^?1, ν₀(ν_2, ³⁵Cl³⁷ClCO) = 568.951791(35) cm^?1 and ν₀(ν₄, ³⁵Cl³⁷ClCO) = 581.758279(35) cm^?1.     

An anharmonic force field for carbonyl sulphide

A 16-parameter force field for OCS based on curvilinear coordinates is presented in table 2 and the agreement between observed and calculated transitions and rotational constants is indicated in tables 4, 5 and 6. The computational approach differs from that of Morino and Nakagawa [2] and similar work on other molecules by other authors, in that perturbation theory is eschewed and the calculated vibrational transitions and rotational constants are derived via the numerical solution of a large matrix. The usual parameters x_ij , y_ijk , α _i ^B and γ _ij ^B are thereby rendered inappropriate intermediates. The approach also leads to estimates of B _e - B ₀ for each isotopic species and thence suggests equilibrium distances r _CO = 1·155386(21) Å and r _CS = 1·562021(17) Å.     

High-resolution spectroscopy of CF2Cl2 in a molecular jet

Absorption spectra of CF₂Cl₂ were recorded around 923 cm^–1, with a resolution of 50 MHz. The application of the molecular jet technique considerably simplifies the spectra as compared to room-temperature experiments. Rotational and vibrational temperatures were measured for CF₂Cl₂ pure and seeded in Ar or He. Molecular constants were obtained for thev ₆ vibrational band of the two most abundant chlorine isotopic species, as well as vibrational band origines for thev ₆±v ₄ and thev ₆±v ₅ hot-bands of the CF₂ ³⁵Cl₂ isotope.Guest     

Theoretical determination of the vibrational levels of NH+ 3 and its isotopomers

The vibrational levels associated with the electronic ground state X²A₂″ of NH⁺ ₃ have been determined up to 5000 cm^?1 by perturbation and variational calculations with full dimensionality of the molecule. For the variational part a new version of MULTIMODE was used which uses the ab initio electronic energy and its first derivative to define the potential energy function. These quantities were generated by the B97-1 density functional and RCCSD(T) approaches. For ND⁺ ₃, ND₂H⁺ and NDH⁺ ₂ the vibrational levels were calculated only by perturbation theory. The rotational constants for all the isotopomers were determined and the first transition dipole moments for NH⁺ ₃ and ND⁺ ₃ were plotted. A critical comparison of the perturbation and variational techniques suggests a possible further modification to the MULTIMODE algorithm for large systems.