The structure of carbodiimide,HNCNH

An experimentally determined r _s -type structure of HNCNH is reported: r _NH = 1.0074 Å, r _CN = 1.2242 Å, ∠HNC = 118.63°, ∠NCN = 170.63°, ∠HN ··· NH = 88.99°. The number of digits quoted allow for errors with two significant figures. In order to obtain these values we recorded rotational—torsional spectra of HN¹³CNH, H¹⁵NC¹⁵NH and DNCND, by using isotopically enriched cyanamide. A chemical equilibrium exists between carbodiimide, HNCNH, and the more stable isomer cyanamide, H₂NCN, which strongly favours cyanamide (approximately 1:115 at 110 °C). The expensive C- and N-substituted isotopomers could only be investigated in the millimetre wave region, while for DNCND the far infrared spectrum between 10–350 cm^?1 was also recorded. Rotational constants of the three isotopomers, as well as of the parent species, were determined by fitting the assigned spectral transitions to the Watson Hamiltonian in S reduction. Using fitting programs written by Schwendeman and Rudolph, r _o, r_s and r^ρ _m structures of HNCNH were derived. The experimentally determined structural parameters are compared with an ab initio r_e structure.     

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.     

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.     

Geometry,strength of binding and Br2 charge redistribution in the complex OC ··· Br2 determined by rotational spectroscopy

The ground-state rotational spectra of the six isotopomers ¹⁶O¹²C ··· ⁷⁹Br⁷⁹Br, ¹⁶O¹²C ··· ⁸¹Br⁷⁹Br, ¹⁶O¹²C ··· ⁸¹Br⁸¹Br, ¹⁶O¹²C ··· ⁷⁹Br⁸¹Br, ¹⁶O¹³C ··· ⁷⁹Br⁷⁹Br, ¹⁶O¹³C ··· ⁸¹Br⁷⁹Br, were observed by pulsed-nozzle, Fourier-transform microwave spectroscopy. The spectroscopic constants B _O, D _J, χ _aa (Br_i), χ _aa (Br_o), M_bb (Br_i) and M _bb (Br_o), where i = inner and o = outer, were determined for each isotopomer. The complex is linear, with the weak bond between the C atom of CO and Br_i. The rotational constants were used to determine the distance r(C ··· Br_i) = 3.1058Å and to show that the Br—Br bond lengthens by ～0.005–0.01Å on complex formation. The intermolecular stretching force constant kσ = 5.0 Nm^?1 was obtained from D_J and the Br nuclear quadrupole coupling constants were interpreted to reveal that a fraction δ = 0.02 of an electronic charge is transferred from Br_i to Br_o when Br₂ is subsumed into the complex. Properties of the two series OC ··· XY and H₃N ··· XY, where XY = C1₂, Br₂ and BrC1, are compared.     

Microwave spectrum and substitution structure of methylene chloride

The microwave spectrum of methylene chloride has been reinvestigated in order to obtain a complete substitution (r_s) structure of well-defined precision. Measurements on the ¹³CH₂Cl₂ species have yielded the following rigid-rotor rotational constants: A = 30746.20 ± 0.10 MHz, B = 3320.63 ± 0.11 MHz, and C = 3053.44 ± 0.10 MHz. These data, combined with revised values reported earlier for other isotopic species, yields the following r_s structural parameters: CCl = 1.767 ± 0.002 Å, CH = 1.085 ± 0.002 Å, ∠HCH = 112.1 ± 0.2°, and ∠ClCCl = 112.2 ± 0.1°.     

Predissociation and photodissociation of IBr

The observed predominance of excited Br(² P _1/2) atoms in the nearultra-violet photodissociation products of IBr is shown to be quantitatively consistent with an intermediate coupling regime in the visible absorption region, which invalidates the traditional interpretation of the B′(O ⁺) state as a new Born-Oppenheimer state arising from a strongly avoided potential curve crossing. A general theory of predissociation at intermediate coupling, covering the positions, intensities and widths of the spectral lines, shows that both diabatic and adiabatic characteristics must be taken into account. The presence of a sharp level is predicted at any coincidence between an adiabatic and a diabatic term value with the same J value, and the spacing between neighbouring lines is shown to depend on an average between the diabatic and adiabatic rotational constants. The theory is successfully applied to the B(³Π _{o ⁺} ) and B′(O ⁺) states of IBr, and potential curves for the two states are reported. The analysis is consistent with the following curve crossing parameters r_x = 3·220 Å, E_x = 16 915 cm^-1, V ₁₂ = 170 cm^-1, and ΔF = 9178 cm^-1 Å^-1, and with the following spectroscopic constants for the B′(O ⁺) state of IBr⁷⁹:

     

Rotational band contours in the 5000 Å 1 B 1g -1 Ag electronic system of p-benzoquinone

Using the technique of computer simulation of rotational band contours the 1–0 band in v ₇, band E, in the 5000 Å ¹ B _1g -¹ A_g system of p-benzoquinone has been rotationally analysed. It is a type A band and the excited state rotational constants are:

The excited state inertial defect determined from these constants is -0·8 ± 0·2 uÅ ². This value is almost certainly due not to non-planarity of the excited state but to a Coriolis interaction between v ₇ and perhaps the b _1u vibration v ₁₃. Such an interaction, if it were weak, would affect only the A′ rotational constant.

Previous assignments [2] of other type A bands and type B bands in the spectrum are reviewed where possible with the new evidence of the computed contours and the assignments remain largely unaltered.     

Ab initio calculation of force constants for the linear molecules HCN,FCN, (CN)2 and the ion N2F+

Force constants have been calculated from ab initio Hartree-Fock wave-functions by the force method, using 7s3p/1 and 5s2p/1 gaussian basis sets for HCN, FCN, C₂N₂ and FN₂ ⁺. Agreement of the quadratic and some cubic force constants with experiment is good for HCN and FCN. The influence of anharmonicity upon the l-type doubling constant of FCN is estimated. Both the experimental l-type doubling constant and the ab initio calculations indicate that the quadratic stretch, stretch coupling constant is positive in FCN, contrary to recent results of Wang and Overend, obtained from the Anderson potential function. There is good agreement for the CN, C′N′ coupling in C₂N₂ but the calculated CN, CC coupling, although positive, is much lower than in two recent experimental force fields. The calculated FN, NN coupling in FN₂ ⁺ is small and positive. The predicted geometry of FN₂ ⁺ is r _NF = 1·28 Å, r _NN = 1·10₅ Å. The validity of the Anderson potential function is discussed.     

Determination of A 0 for CH3F from ground-state combination differences

The direct determination of the ground-state rotational constants A ₀ and D ₀ ^K of methyl fluoride has been accomplished through ground-state combination differences including perturbation-allowed transitions. The values found are A ₀ = 5·182009 ± 0·000012 and D ₀ ^K = (70·33 ± 0·25) × 10^-6 cm^-1. The ‘ normal ’ GSCD have also been used, in conjunction with microwave transitions, to yield improved values for the other rotational constants, including values for H ₀ ^{J K} and H ₀ ^KJ .     

Theoretical rovibrational spectroscopy beyond fc-CCSD(T): the cation CNC+

An accurate near-equilibrium potential energy surface (PES) for CNC⁺ is constructed based on a high-level composite ab initio method. By combining explicitly correlated all-electron CCSD(T)-F12b with scalar relativistic effects and higher order correlation up to coupled cluster theory with singles, doubles, triples and quadruples (CCSDTQ) we achieve convergence in the wavenumbers of the fundamentals to ca. 1 cm^?1. Rovibrational energies are calculated in a variational approach and vibrational term energies and rotational constants are in excellent agreement with available experimental data. Accurate values for centrifugal distortion constants of CNC⁺ in different vibrational states are predicted. Especially the centrifugal distortion constants in the vibrational ground state of D₀ = 0.563 · 10^?6 cm^?1 and H₀ = 0.188 · 10^?10 cm^?1 should be superior to experimentally derived values. Reassignments of some experimentally observed transitions are suggested based on a comparison of experimental and calculated term differences. The bending part of the PES appears to be almost quartic and the band origin of the bending vibration is predicted at 94.2 cm^?1. Absolute line intensities are calculated for various transitions in CNC⁺. For the bending vibration, an intensity is predicted that is three orders of magnitude smaller than for the antisymmetric stretching vibration.     

A partial analysis of rotational structure in the 2710 Å system of p-fluorotoluene

The region of the 0-0 band of the 2710 Å system of p-fluorotoluene has been photographed at high resolution.

The rotational contour of the 0-0 band has been interpreted using two approximations in computed contours: (i) treating the molecule as a symmetric top with free internal rotation, and (ii) treating it as a rigid asymmetric top. The first approximation has enabled an estimate of AT' to be made where AT is the rotational constant of the methyl group about the top axis: the second approximation resulted in valves of AF', B' and C', where AF is the A rotational constant of the ring, although to a rather lower accuracy than has been the case in other substituted benzenes.

Interpretation of the rotational constants shows that in the excited state the methyl group has closed up a little: two extreme interpretations of the constant AT' result in either a decrease in the HCH angles of 1·2±0·7° or a decrease in the C-H bond-lengths of 0·009 ± 0·005 Å. The values of AF', B' and C' indicate that the C-CH₃ bond contracts by about 0·03 Å. This suggests a considerable increase in hyperconjugation in the excited state of p-fluorotoluene compared to the ground state.

The 0-0 band was found to be a type B band implying a polarization of the electronic transition moment along the short in-plane axis. The origin of the band was found to be at 36 859·6±0·3 cm^-1.     

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.     

The microwave spectrum and rotational structure of the Δ and Σ electronic states of sulfur monoxide

The spectrum of ¹Δ and ³Σ SO has been studied in the millimeter and submillimeter region of the microwave spectrum. This expanded spectral coverage has made possible the measurement of twenty-two previously unobserved transitions, several of which are necessary for an accurate calculation of the energy levels. As a result, it is now possible to calculate the rotational transitions between energy levels for which J ≤ 10 in both the ground ³Σ electronic state and the excited ¹Δ electronic state to an accuracy comparable to that of the microwave measurements themselves ( 1 MHz). Among the molecular constants calculated are; for the ¹Δ state: B₀ = 21 295.405 MHz, D₀ = 0.0350 MHz, ω_e = 1108 cm⁻¹, and r₀ = 1.4920 Å; and for the ³Σ state: B₀ = 21 523.561 MHz, D₀ = 0.03399 MHz, λ₀ = 158 254.387 MHz, γ₀ = −168.342 MHz, ₀ = 0.305 MHz, r₀ = 1.4840 Å, B_e = 21 609.552 MHz, λ_e = 157 779.2 MHz, and r_e = 1.4811 Å.     

The microwave spectrum,structure, and quadrupole coupling constants of boron chloride difluoride,BCIF2

The microwave spectrum of boron chloride difluoride, BClF₂, has been investigated in the region 26.5–40.0 GHz. R-branch transitions belonging to the isotopic species ¹¹B³⁵Cl¹⁹F₂, ¹¹B³⁷Cl¹⁹F₂, and ¹⁰B³⁵Cl¹⁹F₂ have been observed and the derived rotational constants yield the following ground-state structural parameters: $\text{r}{}^0\text{(BF) = 1.315 ± 0.006}\text{A}\text{?}$, $\text{r}{}^{\mathrm{s}}\text{(BCl) = 1.728 ± 0.009}\text{A}\text{?}$, < FBF = 118.1 ± 0.5°. The ground-state rotational constants of the most abundant species ¹¹B³⁵Cl¹⁹F₂ are: A₀ = 10 449.32 ± 0.13, B₀ = 4705.811 ± 0.020, C₀ = 3239.702 ± 0.026 MHz, Δ_JK = 8.9 ± 1.7, and Δ_J = 1.86 ± 0.48 KHz. The asymmetry parameter κ = ?0.593291 and the inertial defect δ⁰ = 0.2361 amu Ų which is consistent with that expected for this type of molecule if planar. The ³⁵Cl quadrupole coupling constants for ¹¹B³⁵Cl¹⁹F₂ are χ_aa = ?42.8 ± 1.0, χ_bb = 30.2 ± 1.5, χ_cc = 12.6 ± 1.5 MHz with the asymmetry parameter η = 0.41.     

The bond force constants of graphene and benzene calculated by density functional theory

Stretching (k_r) and bending (k_θ) bond force constants appropriate to describe the bond stiffness of graphene and benzene are calculated using density functional theory. The effect of employing different exchange-correlation functionals for the calculation of k_r and k_θ is discussed using the generalised gradient approximation (GGA) and the local density approximation (LDA). For benzene, k_r = 7.93 mdyn Å^-1 and k_θ = 0.859 mdyn Å rad^-2 using LDA, while k_r = 7.67 mdyn Å^-1 and k_θ = 0.875 mdyn Å rad^-2 using GGA. For graphene, k_r = 7.40 mdyn Å^-1 and k_θ = 0.769 mdyn Å rad^-2 using LDA, while k_r = 6.88 mdyn Å^-1 and k_θ = 0.776 mdyn Å rad^-2 using GGA. This means the difference between the bond force constants for benzene and graphene can be as large as ～12%. The comparison between these two systems allows for elucidation of the effect of periodicity and substitution of carbon atoms by hydrogen in the stiffness of C–C bonds. This effect can be explained by a different redistribution of the charge density when the systems are subjected to strain. The parameters k_r and k_θ computed here can serve as an input to molecular mechanics or finite element codes of larger carbon molecules, which in the past had frequently assumed the same bond force constants for graphene, benzene or carbon nanotubes.     

The anharmonic force field and equilibrium structure of methane

The anharmonic force field of methane has been refined to fit spectroscopic data from the isotopic species ¹²CH₄, ¹³CH₄, ¹²CH₄, ¹²CH₃D, ¹²CHD₃ and ¹²CH₂D₂. Six of the thirteen cubic force constants have been determined experimentally, the remaining cubic constants being fixed at values derived from ab initio calculations. The quartic force field is very crude, in that only f_rrrr has been refined. It is concluded however that the cubic and quartic force fields, even though they are subject to limitations, provide a considerable improvement in the experimental determination of the r _e structure and the quadratic force field. The equilibrium bond length is found to be r _e(CH) = 1·085₈ ± 0·001 Å.     

On the Kirkwood theory of natural optical activity

Vibration-rotation intensities have been calculated for transitions between states of arbitrary vibrational symmetries, for tetrahedral molecules. For this purpose eigenfunctions of first order Coriolis interactions, which are assumed to be much smaller than anharmonic splittings, have been used. While some bands, among which fundamentals and overtones, follow the ΔR = 0 selection rule, for others the most intense vibration-rotation lines are those with ΔR maximum, in agreement with our double-resonance investigations of stretching levels of methane. One such investigation is presented here, in which the lower (3v₃, F ₂) level of CH₄ has been found at 8906·78 cm^-1, in close agreement with local-mode predictions. Several I.R. lines in this region have been assigned, the effective rotational constants being 5·214 and 5·24 cm^-1 for R = J and R ≠ J Coriolis sublevels respectively.     

Evidence for slow exchange in E.S.R. spectra of nitroxide biradicals

Force constants have been calculated for H₂NF and HNF₂ from ab initio Hartree-Fock wavefunctions by the force method, using 7s3p/1 gaussian basis sets. The force field of HNF₂, obtained from a combination of the theoretical results with the experimental frequencies, can be considered as the most reliable one at present. Previous force fields are discussed critically. From a full optimization the predicted geometry of H₂NF is: NF = 1·399 Å, NH = 1·018 Å, HNF = 102·9° and HNH = 105·9°.     

Rotational analysis of the B-X band system of the SbO molecule

Rotational analyses of the two 0-0 bands of theB ²ΣX ²Π_reg system of SbO were carried out for the first time from spectrograms taken in the second order of a 21 ft. concave grating spectrograph having a dispersion of 1·25 Å/mm. The rotational constants of the ν=0 vibrational levels of the upper and lower states, and of the coupling constant A₀ of the lower²Π_reg state were deduced. These values are summarised below. v₀₀=25 334·93 cm^?1 B′₀=0·3190 cm^?1 B″₀=0·3490 cm^?1 A ₀=2276 cm^?1 r′₀=1·933 Å r″₀=1·848 Å.