Ab initio anharmonic force field and equilibrium structure of propene

The quadratic, cubic and semi-diagonal quartic force field of propene has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-ζ quality and a core correlation correction. The experimental mass-dependent r_m structures are also determined and their accuracy is discussed. The use of isolated CH stretching frequencies is shown to be a good method to determine CH bond length.     

Ab initio anharmonic force field and equilibrium structure of vinyl bromide

The quadratic, cubic, and semi-diagonal quartic force field of vinyl bromide has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality including a relativistic pseudopotential on bromine. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality and an offset correction. The experimental mass-dependent r_m structures are also determined and their accuracy is discussed.     

Rotational spectrum, structure and internal rotation in CH3CCl3

The rotational spectra of the v₆ = 1 and v₆ = 2 torsional states of CH₃C³⁵Cl₃ have been measured in the millimeterwave range and accurate spectroscopic constants have been determined. The equilibrium structure, the torsional frequency and the barrier to internal rotation have been calculated ab initio. These results are shown to be compatible with the absence of splittings in the rotational spectra.     

Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

The rotational spectrum of phosphaethene (CH₂PH) was reinvestigated. One hundred and nineteen new lines were measured in the submillimeter range from 500 to 650 GHz. The determination of the centrifugal distortion constants is significantly improved. As the molecule is close to symmetric prolate top, both reduction A and S were compared. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-zeta quality and a core correlation correction. The structure of CH₂PH was compared to that of CH₂NH which was also determined for this goal. It is found that the semi-experimental structure of CH₂NH is less accurate than the ab initio structure. It is also found that the methylene group is much more asymmetric in CH₂NH than in CH₂PH.     

Anharmonic force field and equilibrium structure of nitric acid

The quadratic, cubic and semi-diagonal quartic force field of nitric acid has been calculated at the CCSD(T) level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. It is found that the A and B semi-experimental equilibrium rotational constants of the ¹⁸O isotopologues (for which the rotation of principal axes is large) cannot be accurately reproduced. This problem is discussed and a remedy is proposed. Finally, the semi-experimental structure is in agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of at least quadruple-ζ quality and a core correlation correction, except for the long NO single bond for which the CCSD(T) value is too short due to inadequate treatment of electron correlation. The empirical structures are also determined and their accuracy is discussed. The best equilibrium structure is: r_e(NO_syn) = 1.209(1) Å, r_e(NO_anti) = 1.194(1) Å, r_e(NO) = 1.397(1) Å, r_e(OH) = 0.968(1) Å, ∠(ONO_syn) = 115.8(1)°, ∠(ONO_anti) = 114.2(1)° and ∠(NOH) = 102.2(1)°.     

Ab initio anharmonic force field and equilibrium structure of carbonyl chlorofluoride

The quadratic, cubic, and semi-diagonal quartic force field of OCFCl has been calculated at the MP2 level of theory employing a basis set of triple-zeta quality. The spectroscopic constants derived from the force field are in excellent agreement with those from previous and new experiments. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory. This good agreement indicates that the derived structure is accurate. The equilibrium geometry is: r_e(CO)=1.173(1) Å; r_e(C-F)=1.323(1) Å; r_e(C-Cl)=1.721(1) Å; ∠_e(OCF)=124.0 (1)°; and ∠_e(OCCl)=126.4(1)°.     

Rotational spectra of isotopic species of SO2F2: experimental and ab initio structures

The rotational spectra of ³⁴SO₂F₂ and S¹⁸O¹⁶OF₂ have been measured in their ground vibrational state between 9 and 110 GHz. Accurate rotational constants have been derived. Various experimental structures including the average structure have been determined. The ab initio structure has been calculated at the CCSD(T) level of theory. The different structures are compared and the best equilibrium structure is the ab initio structure: r_e(SO)=1.401 (3) Å, r_e(SF)=1.532 (3) Å, ∠_e(OSO)=124.91(20)°, ∠_e(FSF)=95.53 (20)°.     

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.     

Ab initio anharmonic force field and equilibrium structure of vinyl fluoride and vinyl iodide

The quadratic, cubic and semi-diagonal quartic force field of vinyl fluoride and vinyl iodide have been calculated at the MP2 level of theory employing a basis set of triple-ζ quality including a relativistic pseudopotential on iodine. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality. Finally, the structure of different vinyl derivatives is compared.     

Ground state rotational spectrum,K = 3 splittings,ab initio anharmonic force field and equilibrium structure of trifluoroamine

The submillimetre-wave spectrum of ¹⁴NF₃ has been measured and the ground state rotational spectrum has been reanalysed, including the K=3 splittings. The quadratic, cubic and semidiagonal quartic force field has been calculated at the CCSD(T) level of theory employing a basis set of at least polarized valence triple-zeta quality. This force field has been used to predict the spectroscopic constants, including the parameters specific to the doubly degenerate vibrational states. 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 semiexperimental structures are in excellent agreement with the ab initio equilibrium geometry.     

Microwave and high resolution infrared spectra of vinyl chloride, ab initio anharmonic force field and equilibrium structure

The quadratic, cubic, and semi-diagonal quartic force field of vinyl chloride has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality. The spectroscopic constants derived from this force field are compared with the experimental values. To make this comparison more complete, the rotational constants of the lowest excited state, v₉ = 1 at 395 cm⁻¹ have been determined by microwave spectroscopy and the ν₁₂ band (around 618 cm⁻¹) has been investigated by high-resolution infrared Fourier transform spectroscopy. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-ζ quality and a core correlation correction. The experimental mass-dependent r_m structures are also determined and their accuracy is discussed. The recommended equilibrium geometry is: r (CC) = 1.3262(10), r (CCl) = 1.7263(10), r (CH_g) = 1.0784(10), r (CH_c) = 1.0795(10), r (CH_t) = 1.0797(10), ∠(CCCl) = 122.77(10)°, ∠(CCH_g) = 123.86(10)°, ∠(CCH_c) = 121.80(10)°, ∠(CCH_t) = 119.29(10)°.     

Rotational spectrum and structure of asymmetric dinitrogen trioxide, N2O3

The rotational spectra of the ground vibrational state and the ν₉ = 1 torsional state have been reinvestigated and accurate spectroscopic constants have been determined. The torsional frequency, ν₉ = 70(15) cm⁻¹, has been determined by relative intensity measurements. The assignment of the infrared spectrum has been slightly revised and an accurate harmonic force field has been calculated. The equilibrium structure has been determined using different, complementary methods: experimental, semi-experimental and ab initio, leading to r(NN) = 1.870(2) Å, in particular.     

Ab initio potential energy surface and pressure broadening coefficients for the He-CH3F complex

Symmetry-adapted perturbation theory has been applied to compute the He-CH₃F potential with the CH₃F molecule assumed rigid. The potential has a global minimum of −48.9 cm⁻¹ at the center of mass separation of 7.2 bohr with the helium atom lying along the C-F bond on the hydrogen’s side. The computed points were fitted to an analytic energy surface with a correct asymptotic behaviour. This potential has been used to compute the pressure broadening (PB) coefficients for the (j, k) = (0, 0) → (1, 0) and (1, 0) → (2, 0) rotational transitions of CH₃F perturbed by helium for a wide range of temperatures. Close-coupling results are compared with the experimental data of Willey et al. [J. Chem. Phys. 97 (1992) 4723], Beaky et al. [J. Mol. Struct. 352/353 (1995) 245] and infinite order sudden results are compared with those of Grigoriev et al. [J. Mol. Struct. 186 (1997) 48] for the ν₆ band of CH₃F perturbed by helium at room temperature. To our knowledge, present work is the first attempt of making fully ab initio calculations of collisional cross-sections and pressure broadening coefficients for this simple symmetric top system at low and room temperature.     

Microwave spectrum and structure of methyl phosphonic difluoride

The rotational spectrum of methyl phosphonic difluoride has been reinvestigated using a pulsed-molecular-beam Fabry-Perot cavity microwave spectrometer. The enhanced resolution of the Fourier transform microwave (FTMW) spectrometer (compared to the original work done in a conventional Stark spectrometer) has allowed the measurement of small A-E splittings of many of the rotational transitions caused by the internal rotation of the methyl top. The barrier to internal rotation, V₃ = 676 (25) cm⁻¹, has been determined experimentally from the A-E splittings of the rotational transitions in the ground vibrational state. This barrier height is substantially lower than the previously determined value for the barrier, which was 1252 (14) cm⁻¹. High-level ab initio calculations at the MP2/aug-cc-pVTZ level predict a barrier to internal rotation of 638 cm⁻¹, in agreement with the experimentally determined value found here. The high sensitivity of the FTMW spectrometer has also permitted the measurement of the ¹³C and ¹⁸O isotopomers in natural abundance. The addition of these two isotopomers has allowed an improved structural determination.     

The Equilibrium Structure of Silyl Fluoride

The experimental equilibrium structure of silyl fluoride has been determined using new sets of accurate rotational constants that have recently been obtained by taking into account the most important interactions between the excited vibrational states. The equilibrium structure has also been calculated at the CCSD(T) level of theory with the cc-pVQZ+1 basis set (including corrections for the core correlation). The anharmonic force field up to semidiagonal quartic terms has been calculated at the MP2 level of theory and the equilibrium structure has been derived from the experimental rotational constants and the ab initio rovibrational interaction parameters. Finally, the average structure of both ²⁸SiH₃F and ²⁸SiD₃F has been reevaluated and used to derive the equilibrium structure. These structures are compared and the experimental structure is found to be in slight disagreement with the other ones. The preferred structure is obtained by calculating the median value of the different structures. The results are r_e(SiF)=1.5907 (9) Å, r_e(SiH)=1.4696 (13) Å, ∠_e(HSiF)=108.32(15)°, and ∠_e(HSiH)=110.60(14)°.     

Vibrational energy levels of methyl chloride calculated from full dimensional ab initio potential energy surface

The vibrational levels for two isotopic species of methyl chloride have been calculated in the region 0-3500 cm⁻¹ from the ab initio potential energy surface (PES). The isotopic shift of vibrational levels of molecules ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl has been calculated. The correlation consistent basis sets cc-pVTZ and cc-pVQZ are employed to calculate energy values for 7957 and 3758 points correspondingly from a large domain of the nine-dimensional internal coordinate space. The analytic global PES is fitted with the standard deviation of 4.5 cm⁻¹.     

Ground-state constants, ab initio anharmonic force field, and equilibrium structure of F2BOH

The millimeterwave spectra of F₂¹⁰BOH and F₂¹¹BOH (difluorohydroxyborane) have been measured in their ground vibrational state. Accurate rotational and centrifugal distortion constants have been determined. The equilibrium geometry and anharmonic force fields have been calculated at the CCSD(T) level of theory. The ab initio centrifugal distortion constants and rotation-vibration interaction constants are compared to the experimental values. Some discrepancies are found and discussed. Particularly, it is explained why the semi-experimental structure is not reliable. The best equilibrium structure is: r_e(BF_cis) = 132.29 pm, r_e(BF_trans) = 131.29 pm, r_e(BO) = 134.48 pm, r_e(OH) = 95.74 pm, ∠_e(FBF) = 118.36°, ∠_e(F_cisBO) = 122.25°, and ∠_e(BOH) = 113.14°.     

The microwave spectrum of cyanophosphine, H2PCN

The rotational spectra of cyanophosphine, H₂PCN, have been measured between 10 and 42.5 GHz by Fourier transform microwave spectroscopy. The rotational constants, centrifugal distortion constants, the ¹⁴N quadrupole coupling constant, and the nuclear spin-rotation coupling constants of ³¹P have been determined. Density functional ab initio calculations were performed, and the calculated values of the molecular constants are in excellent agreement with our experimentally determined results. The spectra of three isotopomers were measured, H₂P¹²C¹⁴N, H₂P¹³C¹⁴N, and H₂P¹²C¹⁵N. The derived r₀ structure is quite comparable to the ab initio predicted H₂PCN equilibrium geometry.     

The Lamb-dip spectrum of the J + 1 ← J (J = 0, 1, 3-8) transitions of HCN: The nuclear hyperfine structure due to H, C, and N

The pure rotational J + 1 ← J transitions, with J = 0, 1, 3-8, of H¹³CN have been observed in the millimeter- and submillimeter-wave region using the Lamb-dip technique to resolve the hyperfine structure due to H, ¹³C, and ¹⁴N. The present observations allow us to provide for the first time the spin-rotation constant of ¹³C and the spin-spin interaction constant S₁₂ (between H and ¹³C) as well as to remarkably improve the quadrupole coupling and spin-rotation constants of ¹⁴N. In addition, a good empirical estimation of C_I(H), based on ab initio calculations, has also been provided. Furthermore, our frequencies together with previous data permit to determine the most accurate ground state rotational parameters known up to now.     

Rotational spectrum of trifluoroacetone

The rotational spectra of 5 isotopologues of 1,1,1-trifluoroacetone have been assigned using pulsed-jet Fourier-transform microwave spectroscopy. All rotational transitions appear as doublets, due to the internal rotation of the methyl group. Analysis of the tunneling splittings using both the principal axis method (PAM) and the combined axis method (CAM) methods allows to determine accurately the height of the threefold barrier to internal rotation of the methyl group, and its orientation, leading to V₃ = 3.28 and 3.10 kJ mol⁻¹, respectively. The r_s geometry of the molecular skeleton, a partial r₀ structure of the molecule and supporting ab initio calculations are also reported.