Pure rotational spectrum, ab initio anharmonic force field, and equilibrium structure of silyl chloride

The ground state rotational spectra of H₃Si³⁵Cl, H₃Si³⁷Cl, and D₃Si³⁵Cl have been measured from the microwave to the submillimeterwave ranges and accurate rotational parameters have been determined. For H₃Si³⁷Cl, they are in good agreement with the values obtained from the ground state combination differences. The quadratic, cubic, and semi-diagonal quartic force field has been calculated at the MP2 level of theory employing a basis set of polarized valence quadruple-zeta quality. This force field has been used to predict the spectroscopic constants. The calculated values are found to be in good agreement with the available experimental data. The equilibrium structure has been derived from the experimental ground state rotational constants and either the ab initio or the experimental rovibrational interaction parameters. These experimental and semi-experimental structures are in excellent agreement with the ab initio equilibrium geometry.     

Comparative spectroscopy with the (d, τ) reaction on even Ar isotopes

The (d, τ) proton pick-up reactions on ³⁶Ar and ³⁸Ar have been studied at an incident energy of 52 MeV. Differential cross sections were measured and spectroscopic factors were extracted for transitions to 14 states of ³⁵Cl and 13 states of ³⁷Cl, respectively. Many new $\text{5}\text{2}$⁺ states and nearly the complete $\text{1}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ strength have been observed in both nuclei. The width of the $\text{1}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ spectral distribution is appreciably smaller for the semi-closed shell nucleus ³⁸Ar than for ³⁶Ar and ⁴⁰Ar. The results are compared with those from the ⁴⁰Ar(d, τ) reaction and proton stripping reactions on each of the three argon isotopes. Recent shell model calculations proved to be well suited to describe excitation energies as well as spectroscopic factors for the low-lying positiveparity states. Mirror relations were established for the nuclei ³⁵Ar and ³⁵Cl. In ³⁷Cl we succeeded in observing a weak component of a 1p proton hole state at a separation energy of only 18 MeV.     

The pure rotational spectrum of ZnCl (XΣ): Variations in zinc halide bonding

The radical ZnCl (X²Σ⁺) has been studied using millimeter-wave direct-absorption techniques. Pure rotational spectra of ⁶⁷Zn³⁵Cl, ⁶⁶Zn³⁷Cl, ⁶⁸Zn³⁵Cl, ⁶⁴Zn³⁵Cl, ⁶⁴Zn³⁷Cl, and ⁶⁶Zn³⁵Cl were measured in the vibrational ground state and data were also recorded for the latter three in the v = 1 and v = 2 states. Every rotational transition was found to be split into a doublet due to spin-rotation interactions. For ⁶⁷Zn³⁵Cl, each doublet exhibited additional splittings arising from hyperfine coupling of the ⁶⁷Zn (I = 5/2) nucleus. Rotational, fine structure, and hyperfine constants have been determined from these data, and equilibrium parameters calculated. The equilibrium bond length of ⁶⁴Zn³⁵Cl is found to be 2.13003305(24) Å, in good agreement with recent theoretical predictions. Interpretation of hyperfine constants indicates that the 12σ orbital is ∼70% Zn(4s) in character, suggesting that the zinc chloride bond is relatively ionic.     

The high-resolution infrared spectra of the ν2 and ν3 bands of HOCl

The infrared spectra of the a-type transitions of the ν₂ and ν₃ bands of HO³⁵Cl and HO³⁷Cl have been obtained under high resolution. Line assignments of both bands have been made, and the spectroscopic constants have been obtained for both bands using a Watson Hamiltonian. Lines of the K_a = 5 subband of the ν₂ band of the HO³⁵Cl molecule were found to be slightly shifted by an interaction with the K_a = 4 level of the 2ν₃ vibrational state. The b-type transitions permitted for both bands were too weak to observe. Relative intensities of selected lines of both bands have been measured, and empirical Herman-Wallis factors have been determined.     

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).     

Infrared emission spectrum and potential constants of HCl

The emission spectrum from a low-pressure hydrogen chloride flame has been recorded in the 3.1–5.3 μm region at high resolution using a 4.5-m grating spectrometer coupled to a PDP-15 computer. The data obtained for the v → v - 1 band sequence, with v = 1 to 6 for H³⁵Cl and v = 1 to 5 for H³⁷Cl, were combined with other accurate data and analyzed to obtain the vibrational and rotational constants and Dunham coefficients for the H³⁵Cl and H³⁷Cl molecules. Using this information, eighth-order nonlinear least-squares estimates of the Dunham, Simons-Parr-Finlan, Ogilvie, and Sandeman potential constants were computed. While the values of all four sets of constants display a lack of convergence, the constants of Sandeman's expansion exhibit better statistical behavior than the other three. This suggests that a Sandeman-like inversion of the Simons-Parr-Finlan and Ogilvie potential constants would be worthwhile.     

The microwave spectrum of isotopically substituted hypochlorous acid: Determination of the molecular structure

Microwave spectra have been measured for four isotopically substituted species of hypochlorous acid (D¹⁶O³⁵Cl, D¹⁶O³⁷Cl, H¹⁸O³⁵Cl, H¹⁸O³⁷Cl). Both a- and b-type transitions have been analyzed for rotational, centrifugal distortion, and Cl nuclear quadrupole coupling constants. The distortion constants, together with vibrational wavenumbers, have been used to evaluate a valence harmonic force field. Effective, substitution, ground state average, and estimated equilibrium structures are presented.     

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.     

Rotational spectra, nuclear quadrupole hyperfine tensors, and conformational structures of the mustard gas simulent 2-chloroethyl ethyl sulfide

Rotational spectra have been recorded for both the ³⁵Cl and ³⁷Cl isotopic forms of two structural conformations of 2-chloroethyl ethyl sulfide (CEES). The rotational constants of the ³⁵Cl and ³⁷Cl isotopomers were used to identify the conformational isomers. A total of 236 hyperfine transitions have been assigned for 47 rotational transitions of the ³⁵Cl isotope of a GGT conformer, and 146 hyperfine have been assigned for 37 rotational transitions of the ³⁷Cl isotopomer. For the second conformer, a total of 128 (110) hyperfine and 30 (28) rotational transitions have also been assigned to the ³⁵Cl (³⁷Cl) isotopes of a TGT conformation. The extensive hyperfine splitting data, measured to high resolution with a compact Fourier transform microwave spectrometer, were used to determine both the diagonal and off-diagonal elements of the ³⁵Cl and ³⁷Cl nuclear quadrupole coupling tensors in the inertial tensor principal axis system. The experimental rotational constant data, as well as the ³⁵Cl and ³⁷Cl nuclear quadrupole coupling tensors, were compared to the results from 27 optimized ab initio (HF/6-311++G^∗∗ and MP2/6-311++G^∗∗) model structures.     

The α-transfer reactions 27Al(6Li,d)31P, 29Si(6Li,d)33S and 31P(6Li,d)35Cl at 36 MeV

The α-transfer reactions ²⁷Al(⁶Li, d)³¹P, ²⁹Si(⁶Li, d)³³S and ³¹P(⁶Li, d)³⁵Cl have been studied at a ⁶Li energy of 36 MeV. Absolute cross sections and angular distributions have been measured and an exact finite-range distorted-wave Born approximation analysis assuming a direct cluster transfer has been used to extract from the data α-particle spectroscopic strengths for levels populated in ³¹P, ³³S and ³⁵Cl in the three reactions respectively. The results show that in the case of most of the low-lying excited states of ³¹P, a single value of L of the transferred α-particle contributes, though a multiplicity of L-values are allowed by angular momentum selection rules. It is also found that the α-particle spectroscopic strength of the ground state of ³¹P is a factor of 2 more than the strengths of the ground states of ³³S and ³⁵Cl. The α-spectroscopic strengths of ground states of these, as well as other odd-A s-d shell nuclei, are compared with the presently available shell model calculations.     

Microwave spectra of eight isotopic modifications of 1-chloro-1-fluoroethylene

The rotational spectra of eight isotopomers of 1-chloro-1-fluoroethylene in the 6-22 GHz region have been collected and analyzed. Each rotational transition is split into hyperfine components by the chlorine (either ³⁵Cl or ³⁷Cl) nuclear quadrupole coupling interaction and additionally, one or more smaller interactions such as the spin-rotation interaction due to the fluorine atom, hydrogen-hydrogen spin-spin coupling interactions, and in appropriately substituted species, the deuterium nuclear quadrupole hyperfine interaction. The rotational constants derived from these isotopomers allow the determination of average and Kraitchman substitution structures for 1-chloro-1-fluoroethylene, whereas the availability of the diagonal chlorine nuclear quadrupole coupling constants for all the isotopomers provides complete quadrupole coupling tensors for both ³⁵Cl and ³⁷Cl. In the course of this work, the rotational spectrum of an excited vibrational state of the normal isotopomer was observed, which ab initio calculations suggest should be assigned to ν₉=1, an in-plane bending motion at the CFCl end of the molecule.     

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.     

Microwave spectrum and molecular force field of tetratomic C2v molecules: NO2Cl

The rotational constants and quartic centrifugal distortion constants for NO₂³⁵Cl and NO₂³⁷Cl have been determined from an analysis of rotational transitions in the microwave and millimeter wave regions between 8.2–40 and 90–120 GHz, respectively.The values of the in-plane force constants in the general harmonic potential field have been obtained by combination of infrared and microwave data. Vibrational frequencies of ¹⁴NO₂Cl and ¹⁵NO₂Cl, inertia defects of NO₂³⁵Cl in the excited vibrational states v₃ = 1 and v₅ = 1, and first-order centrifugal distortion constants of NO₂³⁷Cl are the experimental data used in the least-squares fitting determination of force constants.     

The microwave and millimeter-wave spectrum of methylchloroform

The microwave and millimeter-wave spectra of methylchloroform, CH₃C³⁵Cl₃, have been reexamined in detail, including the hyperfine structure due to the three ³⁵Cl quadrupolar nuclei. Good values are found for the rotational and centrifugal distortion constants of the ground state and the lowest E state v₁₂ = 1, and values are also given for the weaker A₂ torsional state.     

The microwave spectrum of CHD2Cl

The ground vibrational state microwave spectrum of CHD₂Cl has been studied in the region 26.5–40.0 GHz. From the observation of weak c-type transitions the A₀ rotational constants of CHD₂³⁵Cl and CHD₂³⁷Cl have been determined to be 95 426.08 ± 0.06 and 95 425.23 ± 0.11 MHz, respectively. The observed a-type and c-type transitions have been used to obtain A, B, C, all five quartic and one sextic distortion constants present in the reduced Hamiltonian of Watson for the ³⁵Cl and ³⁷Cl isotopic modifications of CHD₂Cl.     

Microwave spectra of the Cl and Cl isotopomers of dichloromethylene: Nuclear quadrupole-, spin-rotation-, and nuclear shielding constants from the hyperfine structures of rotational lines

The rotational spectra of the isotopomers C³⁵Cl³⁷Cl and C³⁷Cl₂ of dichloromethylene in the ground vibronic state were recorded in the range 10-33 GHz using a molecular beam Fourier transform microwave spectrometer. CCl₂ was generated by flash pyrolysis using different precursors. The observed spectra were analyzed to yield rotational and centrifugal distortion constants, as well as the complete Cl nuclear quadrupole coupling tensors and the spin-rotation interaction constants from the hyperfine structure of the rotational lines. With inclusion of data from previous work on the most abundant species C³⁵Cl₂ [N. Hansen, H. Mäder, F. Temps, Phys. Chem. Chem. Phys. (3) (2001) 50-55.] a refined r₀ structure was determined. The spin-rotation interaction constants of all three isotopomers were used to derive ³⁵Cl and ³⁷Cl principal inertial axis nuclear magnetic shielding components which have not yet been determined by NMR spectroscopy.     

Microwave spectrum of 2-chloropyridine

The microwave spectrum of 2-chloropyridine, C₅H₄NCl, has been studied in the frequency range from 26.5–40.0 GHz. The spectrum is characterized by strong parallel type transitions of a near-prolate asymmetric top. The assigned transitions have been used to evaluate the ground state rotational constants of the two chlorine isotopes. The rotational constants are (in MHz): A = 5872.52, B = 1637.83, C = 1280.48 for the ³⁵Cl isotopic species and A = 5872.16, B = 1591.76, C = 1252.17 for the ³⁷Cl isotopic species. The small inertial defect indicates the molecule is planar. In addition an excited vibrational state of C₅H₄N³⁵Cl has been observed and analyzed. The chlorine quadrupolar coupling constants were determined for the ground state and are: χ_aa = ?71.9 MHz for ³⁵Cl and χ_aa = ?54.9 MHz for ³⁷Cl. By assuming the pyridine ring structure the CCl bond length is found to be 1.72 Å.     

Molecular constants for NSCl and NSF

The complete infrared spectrum of gaseous NSCl, including the hitherto unobserved ν₃, is reported. A set of force constants for gaseous NSCl consistent with a number of pieces of independent data such as the isotopic shifts (¹⁴N³²S³⁵Cl, ¹⁵N³²S³⁵Cl, ¹⁴N³²S³⁷Cl, ¹⁵N³²S³⁷Cl, ¹⁴N³⁴S³⁵Cl and ¹⁵N³⁴S³⁵Cl), centrifugal distortion constants (¹⁴N³²S³⁵Cl), and the inertia defect (¹⁴N³²S³⁵Cl) has been computed. Also, the force field of NSF has been redetermined using the vibrational frequencies and the centrifugal distortion constants.     

The microwave spectrum of HGeCl

The J = 1₀₁-0₀₀ and 2₀₂-1₀₁ transitions of nine isotopomers of chlorogermylene, H⁷⁴Ge³⁵Cl, H⁷⁴Ge³⁷Cl, H⁷²Ge³⁵Cl, H⁷²Ge³⁷Cl, H⁷⁰Ge³⁵Cl, H⁷⁰Ge³⁷Cl, H⁷⁶Ge³⁵Cl, H⁷⁶Ge³⁷Cl, and H⁷³Ge³⁵Cl are measured at 8-9 and 16-18 GHz. The effective rotational constants, the nuclear quadrupole coupling constants of ³⁵Cl, ³⁷Cl, and ⁷³Ge, and the nuclear spin-rotation coupling constants of ³⁵Cl and ³⁷Cl are determined.     

Vibration-rotation spectra of deuterated hypochlorous acid and the determination of the equilibrium structure

Vibration-rotation spectra of the three fundamental vibrations of D¹⁶O³⁵Cl have been measured at a resolution of 0.01 cm⁻¹ to determine vibration-rotation constants. From these results values for the equilibrium rotational constants have been established and used, in conjunction with the equilibrium rotational constants for H¹⁶O³⁵Cl (C. M. Deeley and I. M. Mills, J. Mol. Spectrosc. 114, 368–376 (1985)), to determine the equilibrium structure of hypochlorous acid.