The Electrophilicities of XCF3 and XCl (X=H, Cl, Br, I) and the Propensity of These Molecules To Form Hydrogen and Halogen Bonds with Lewis Bases: An Ab Initio Study.

Equilibrium dissociation energies, De , of four series of halogen- and hydrogen-bonded complexes B⋅⋅⋅XCF3 (X=H, Cl, Br and I) are calculated ab initio at the CCSD(T)(F12c)/cc-pVDZ-F12 level. The Lewis bases B involved are N2 , CO, PH3 , C2 H2 , C2 H4 , H2 S, HCN, H2 O and NH3 . Plots of De versus NB , where the NB are the nucleophilicities assigned to the Lewis bases previously, are good straight lines through the origin, as are those for the corresponding set of complexes B⋅⋅⋅XCl. The gradients of the De versus NB plots define the electrophilicities EXCF3 and EXCl of the various Lewis acids. The determined values are: EXCF3 =2.58(22), 1.40(9), 2.15(2) and 3.04(9) for X=H, Cl, Br and I, respectively, and EXCl =4.48(22), 2.31(9), 4.37(27) and 6.06(37) for the same order of X. Thus, it is found that, for a given X, the ratio EXCl / EXCF3 is 2 within the assessed errors, and therefore appears to be independent of the atom X and of the type of non-covalent interaction (hydrogen bond or different varieties of halogen bond) in which it is involved. Consideration of the molecular electrostatic surface potentials shows that De and the maximum positive electrostatic potential σmax (the most electrophilic region of XCF3 and XCl, which lies on the symmetry axes of these molecules, near to the atom X) are strongly correlated.

An investigation of the molecular geometry and electronic structure of nitryl chloride by a combination of rotational spectroscopy and ab initio calculations.

The ground-state rotational spectra of the six isotopomers (16)O(2) (14)N(35)Cl, (16)O(2) (14)N(37)Cl, (18)O(16)O(14)N(35)Cl, (18)O(2) (14)N(35)Cl, (16)O(2) (15)N(35)Cl, and (16)O(2) (15)N(37)Cl of nitryl chloride were observed with a pulsed-jet, Fourier-transform microwave spectrometer to give rotational constants, Cl and (14)N nuclear quadrupole coupling, and spin-rotation coupling constants. These spectroscopic constants were interpreted to give r(0), r(s), and r(m) ((2)) versions of the molecular geometry and information about the electronic redistribution at N when nitryl chloride is formed from NO(2) and a Cl atom. The r(m) ((2)) geometry has r(N-Cl)=1.8405(6) A, r(N-O)=1.1929(2) A, and the angle ONO=131.42(4) degrees , while the corresponding quantities for the r(s) geometry are 1.8489 A, 1.1940 A, and 131.73 degrees , respectively. Electronic structure calculations at CCSD(T)cc-pVXZ (X=T, Q, or 5) levels of theory were carried out to give a r(e) geometry, vibration-rotation corrections to equilibrium rotational constants, and values of the (35)Cl and (14)N nuclear hyperfine (quadrupole and spin-rotation) coupling constants in good agreement with experiment. The equilibrium geometry at the CCSD(T)/cc-pV5Z level of theory has r(N-Cl)=1.8441 A, r(N-O)=1.1925 A and the angle ONO=131.80 degrees . The observed rotational constants were corrected for the vibration-rotation effects calculated ab initio to yield semiempirical equilibrium constants which were then fitted to give the following semiempirical equilibrium geometry: r(N-Cl)=1.8467(2) A, r(N-O)=1.1916(1) A, and the angle ONO=131.78(3) degrees .

Rotational spectrum, inversion, and geometry of 2,5-dihydrofuran...ethyne and a generalization about Z...H-C hydrogen bonds.

The ground-state rotational spectra of nine isotopomers of a complex formed between 2,5-dihydrofuran and ethyne were recorded with a pulsed-jet, Fourier-transform microwave spectrometer. Rotational and centrifugal distortion constants were obtained for C4H6O...HCCH, C4H6O...DCCH, C4H6O...HCCD, C4H6O...DCCD, [3,4-D2]-C4H6O...HCCH, C4H6O...H13CCH, C4H6O...HC13CH, , and [3(13C]-C4H6O...HCCH. The substituted species were studied in their natural abundances. For the more abundant isotopomers, weak c-type transitions as well as strong a-type transitions were observed. The primary intermolecular binding was shown to consist of a hydrogen bond formed by the ethyne subunit acting as the proton donor and the O atom of 2,5-dihydrofuran as the proton acceptor. The complex has a plane of symmetry that includes the O atom and the ethyne subunit, with a pyramidal configuration at oxygen. A fit of the principal moments of inertia of all nine isotopomers under the assumption of unperturbed 2,5-dihydrofuran and ethyne geometries yielded the values r(O...H)=2.127(8) A, phi=57.8(18) degrees , and theta=16.2(32) degrees, where phi is the angle made by the HCCH subunit at O and theta is the angular deviation of the O...H-C nuclei from collinearity. This geometry is compared with those obtained by ab initio calculations conducted with a range of basis sets and with electron correlation taken into account at the MP2 (Møller-Plesset second order) level of theory. A small inversion doubling (approximately equal to 20-30 kHz) of c-type transitions, well resolved only for the parent isotopomer and [3HCCH, was attributed to a vibrational motion that inverts the configuration at oxygen. A one-dimensional model for this motion was used with a double minimum potential energy function of the type V(phi)=alphaphi(4)+betaphi(2) to estimate the observed separation DeltaE(01) of the lowest pair (v=0 and v=1) of associated energy levels. The predicted DeltaE(01) had the same magnitude as that deduced from the inversion doubling of the c-type transitions. The geometry of C4H6O...HCCH is compared with those other B...HCCH, where B is vinyl fluoride, oxirane, and thiirane. A rationalization of the angular geometries of various B...HX, where X=F, Cl, Br, or CCH, is presented.

Structural and electronic properties of the charge-transfer complex H3P...Br2 determined by Fourier transform microwave spectroscopy.

The ground-state rotational spectra of six isotopomers of the symmetric-top complex H3P...Br2 have been measured by the technique of pulsed-nozzle, Fourier transform microwave spectroscopy. The spectroscopic constants B0, DJ, DJK, chiaa(Brx) and Mbb(Brx), x=i (inner) or o (outer) bromine atom, were obtained from analysis of the spectra. Interpretation of these constants with the aid of models revealed that the pre-reactive complex has an intermolecular bond of length r(P...Br) = 3.0440(4) A between the P atom of PH3 and one Br atom of Br2 and that this bond is a relatively strong one, as measured by the intermolecular stretching force constant ksigma-9.8 Nm(-1). The complex was discovered to have a significant contribution from charge transfer in the ground state by establishing the fraction of intermolecular charge transferred from P to Bri[sigmai = 0.077(23)] and the fraction of intramolecular charge transferred from Bri to Bro [sigmap(Br)=0.11(1)].

The nature of the complex formed between pyridine and hydrogen bromide in the gas phase: an experimental approach using rotational spectroscopy.

The rotational spectra of two isotopomers, C(5)H(5)N...H(79)Br and C(5)H(5)N...H(81)Br, of a complex formed by pyridine and hydrogen bromide were observed by using a pulsed-jet, Fourier-transform microwave spectrometer that incorporated a mixing nozzle. Rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants for the (14)N and Br nuclei were determined. The rotational constants indicate that the observed complex has a planar geometry of C(2v) symmetry, with the HBr subunit lying along the C(2) axis of pyridine. These conclusions are in good agreement with those obtained earlier from infrared spectroscopy in cryogenic matrices and ab initio calculations. The distance r(N...H)=1.137(2) A was obtained by fitting the rotational constants under the assumption of an unchanged pyridine geometry and with r(H-Br) fixed at the value obtained through an ab initio calculation. The nuclear quadrupole coupling constants were interpreted, with the aid of ab initio calculations for the complex, as well as hydrogen-bonded and ion-pair limiting models for the interaction of pyridine and HBr, to establish that the complex may be visualized in terms of a substantial contribution (>60%) of the ionic structure C(5)H(5)NH(+)...Br(-) to its valence-bond description. The intermolecular force constant k(sigma)=57.8(16) N m(-1) determined from the centrifugal distortion constants Delta(J) of the two isotopomers is also consistent with a strongly bound complex involving partial proton transfer.

Microwave spectrum and molecular structure of the carbon monoxide-hydrogen bromide molecular complex.

Rotational spectra have been assigned for five isotopic species of the OC...HBr hydrogen-bonded molecular complex by using pulsed microwave Fourier transform spectroscopy in a Fabry-Perot cavity and a pulsed supersonic nozzle as the molecular source. The rotational constants, centrifugal distortion constants, Br nuclear-quadrupole-coupling constants, and Br spin-rotation constants were determined and from them, the vibrationally averaged structure of OCHBr was derived. This structure is consistent with a linear geometry at equilibrium and an atomic arrangement as written above. The intermolecular potential binding CO to HBr is discussed.

Pre-reactive complexes in mixtures of water vapour with halogens: characterisation of H2O...ClF and H2O...F2 by a combination of rotational spectroscopy and ab initio calculations.

Complexes H2O...ClF and H2O...F2 were detected by means of their ground-state rotational spectra in mixtures of water vapour with chlorine monofluoride and difluorine, respectively. A fast-mixing nozzle was used in conjunction with a pulsed-jet, Fourier-transform microwave spectrometer to preclude the vigorous chemical reaction that these dihalogen species undergo with water. The ground-state spectra of seven isotopomers (H2 16O...35ClF, H2 16O...ClF, H2 18O...35ClF, D2 16O... 35ClF, D2 16O...37ClF, HDO...35ClF and HDO...37ClF) of the ClF complex and five isotopomers (H2O...F2, H2 18O...F2, D2O...F2, D2 18O...Fi and HDO...F2) of the F2 complex were analysed to yield rotational constants, quartic centrifugal distortion constants and nuclear hyperfine coupling constants. These spectroscopic constants were interpreted with the aid of simple models of the complexes to give effective geometries and intermolecular stretching force constants. Isotopic substitution showed that in each complex the H2O molecule acts as the electron donor and either CIF or F2 acts as the electron acceptor, with nuclei in the order H2O...ClF or H2O...F2. For H2O...ClF, the angle phi between the bisector of the HOH angle and the O...Cl internuclear line has the value 58.9(16)degrees, while the distance r(O...Cl)= 2.6081(23) A. The corresponding quantities for H2O...F2 are phi = 48.5(21)degrees and r(O...Fi) = 2.7480(27) A, where Fi indicates the inner F atom. The potential energy V(phi) as a function of the angle phi was obtained from ab initio calculations at the aug-cc-pVDZ/MP2 level of theory for each complex by carrying out geometry optimisations at fixed values of phi in the range +/-80degrees. The global minimum corresponded to a complex of Cs symmetry with a pyramidal configuration at O in each. The function V(phi) was of the double-minimum type in each case with equilibrium values phie = +/-55.8degrees and +/-40.5degrees for H2O...ClF and H2O...F2, respectively. The barrier at the planar C2v conformation was V0= 174cm(-1) for H2O...ClF and 7cm(-1) for H2O...F2. For the latter complex, the zero-point energy level lies above the top of the barrier.