Quantum Effects for a Proton in a Low-Barrier, Double-Well Potential: Core Level Photoemission Spectroscopy of Acetylacetone.

We have performed core level photoemission spectroscopy of gaseous acetylacetone, its fully deuterated form, and two derivatives, benzoylacetone and dibenzoylmethane. These molecules show intramolecular hydrogen bonds, with a proton located in a double-well potential, whose barrier height is different for the three compounds. This has allowed us to examine the effect of the double-well potential on photoemission spectra. Two distinct O 1s core hole peaks are observed, previously assigned to two chemical states of oxygen. We provide an alternative assignment of the double-peak structure of O 1s spectra by taking full account of the extended nature of the wave function associated with the nuclear motion of the proton, the shape of the ground and final state potentials in which the proton is located, and the nonzero temperature of the samples. The peaks are explained in terms of an unusual Franck-Condon factor distribution.

Chirped-pulse Fourier transform millimeter-wave spectroscopy of ten vibrationally excited states of i-propyl cyanide: exploring the far-infrared region.

We report here further spectroscopic investigation of the astrochemically relevant molecule i-propyl cyanide. We observed and analysed the rotational spectra of the ground state of the molecule and ten vibrationally excited states with energies between 180-500 cm-1. For this, we used a segmented W-band spectrometer (75-110 GHz) and performed the experiments under room temperature conditions. This approach thus provides access to high-resolution, pure rotational data of vibrational modes that occur in the far-infrared fingerprint region, and that can be difficult to access with other techniques. The obtained, extensive data set will support further astronomical searches and identifications, such as in warmer regions of the interstellar space where contributions from vibrationally excited states become increasingly relevant.

On the ClC halogen bond: a rotational study of CF3Cl-CO.

The rotational spectra of two isotopologues (CF3(35)Cl-CO and CF3(37)Cl-CO) of the CF3Cl-CO adduct have been investigated and analyzed using supersonic-jet Fourier transform microwave spectroscopy, and found to have the features of a symmetric top. Rotational, centrifugal distortion, and nuclear quadrupole ((35)Cl and (37)Cl) coupling constants have been precisely obtained from high-resolution measurements. The two subunits of the complex are held together via a ClC halogen bond interaction. Information on the internal dynamics and the dissociation energy of the complex is provided.

Interactions between Carboxylic Acids and Heteroaromatics: A Rotational Study of Formic Acid-Pyridine.

The rotational spectra of four isotopologues of the 1:1 complex between formic acid and pyridine show that the two units are linked together through a "classical" (OH···N) and a weak (CH···O) hydrogen bond. The molecular system appears quite rigid and no effects of the internal motions have been observed in the spectrum. The dissociation energy obtained from the centrifugal distortion by applying an approximate model, 39.8 kJ/mol, is quite similar to the ab initio value, 41.7 kJ/mol. Its relatively high value suggests a small charge transfer to take place.

Conformational space and photochemistry of tyramine isolated in argon and xenon cryomatrixes.

The infrared spectra of tyramine monomers trapped in low-temperature argon and xenon matrixes were recorded. The presence of the flexible ethylamino side chain gives rise to a complex conformational surface that contains several minima of relatively low energies, some of them stabilized by a weak N-H···π hydrogen bond interaction between the amino group and the phenyl ring. The experimental infrared spectra confirm the presence of at least two stable conformers isolated in the matrixes. Annealing experiments performed on the xenon matrix revealed a change in the relative population of the experimentally relevant conformers upon isolation in this polarizable matrix, compared to the gas phase. The general interpretation of the spectra was based on harmonic and anharmonic quantum chemical calculations, undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) basis set. The photochemical behavior of the matrix-isolated compound upon narrow-band UV irradiation was also investigated. Identification of ketene species in the spectra of the irradiated matrixes suggests the occurrence of a ring-opening reaction, which in the xenon matrix occurs concomitantly with the conformational isomerization of tyramine.

Shapes and internal dynamics of the 1:1 adducts of ammonia with trans and gauche ethanol: a rotational study.

Two 1:1 adducts of ammonia with ethanol have been characterized by using pulsed-jet FT microwave spectroscopy. They are formed with two different (trans and gauche), stable conformers of ethanol. Several internal-dynamics effects are reflected in the features of the rotational spectra. The trans complex shows the tunneling effects owing to internal rotation of both ammonia and the methyl group. The rotational transitions of the gauche species exhibit a small splitting that is related to tunneling through the potential-energy barrier between the two equivalent minima.

The rotational spectra, potential function, Born-Oppenheimer breakdown, and hyperfine structure of GeSe and GeTe.

The pure rotational spectra of 18 and 21 isotopic species of GeSe and GeTe have been measured in the frequency range 5-24 GHz using a Fabry-Pérot-type resonator pulsed-jet Fourier-transform microwave spectrometer. Gaseous samples of both chalcogenides were prepared by a combined dc discharge/laser ablation technique and stabilized in supersonic jets of Ne. Global multi-isotopologue analyses of the derived rotational data, together with literature high-resolution infrared data, produced very precise Dunham parameters, as well as rotational constant Born-Oppenheimer breakdown (BOB) coefficients (δ(01)) for Ge, Se, and Te. A direct fit of the same datasets to an appropriate radial Hamiltonian yielded analytic potential-energy functions and BOB radial functions for the X(1)Σ(+) electronic state of both GeSe and GeTe. Additionally, the electric quadrupole and magnetic hyperfine interactions produced by the nuclei (73)Ge, (77)Se, and (125)Te were observed, yielding much improved quadrupole coupling constants and first determinations of the spin-rotation parameters.

Tautomerism in 4-hydroxypyrimidine, S-methyl-2-thiouracil, and 2-thiouracil.

The keto-enol tautomerism of 4-hydroxypyrimidine and of the related molecules S-methyl-2-thiouracil and 2-thiouracil has been investigated using synchrotron-based techniques. The populations of the constituent tautomers and thermodynamic parameters have been obtained by analysis of core-level photoemission spectra. The effect of substituents on the stability of tautomers has been revealed. Attaching additional OH (or SH) groups to the aromatic ring stabilizes the dioxo (or oxo-thione) forms. However, substitution of hydrogen in position 2 by an S-CH(3) group (that is, in going from 4-hydroxypyrimidine to S-methyl-2-thiouracil) does not significantly affect the tautomeric equilibrium.

The free jet microwave spectrum of 2-phenylethylamine-water.

We observed the rotational spectrum of the 1:1 molecular adduct between 2-phenylethylamine and water (normal and H(2)(18)O species) by free jet absorption microwave spectroscopy in the frequency region 60-78 GHz. The dominant spectrum belongs to the structure where the PEA moiety is in the most stable gauche conformation and the water molecule is hydrogen bound to the nitrogen lone pair. The orientation of the water molecule is such that the oxygen atom is almost equidistant (ca. 2.5 A) from the closest methylenic and aromatic hydrogen atoms.

Rotational and core level spectroscopies as complementary techniques in tautomeric/conformational studies: the case of 2-mercaptopyridine.

Millimeter wave free jet absorption and core level photoemission spectroscopies give complementary and precise information on the conformational/tautomeric equilibrium of 2-mercaptopyridine.

Rotational spectrum of the mixed van der Waals triad pyridine-Ar-Ne.

We report the Fourier transform microwave spectra of four isotopologues of the hetero triad pyridine-Ar-Ne, formed by the combination of two isotopes of the nitrogen atom (14N and 15N) in pyridine with two isotopes of the rare gas (RG) atoms (20Ne and 22Ne), by using pulsed jet spectroscopy. We detected the conformer denoted [1,1], with the Ne and Ar atoms located one on each side of the ring plane. The [2,0] species, with the two RG atoms on the same side of the ring, was not observed. Ab initio MP2/6-311++G** calculations suggest the rotational spectrum of this species to be complicated by the presence of several almost equivalent minima, separated by very low barriers. Four structural van der Waals parameters, R(Ar), R(Ne), theta(Ar) and theta(Ne), which localize the RG atoms with respect to pyridine, are determined. The 14N nuclear quadrupole coupling constants are obtained for the isotopologues containing this nucleus.

Microwave spectrum of [1,1]-pyridine-Ne2.

We investigated the rotational spectra of six isotopologues of pyridine--Ne(2), formed by combinations of two isotopes of the nitrogen atom ((14)N and (15)N) in pyridine with two isotopes of the rare gas atoms ((20)Ne and (22)Ne), by using pulsed jet Fourier transform microwave spectroscopy. We detected the C(2v) symmetry conformer, denoted as [1,1], where the Ne atoms are located one on each side of the ring plane. The [2,0] species, with the two Ne atoms on the same side of the ring, was not observed. Two structural parameters, R and theta, that localize the rare gas atoms with respect to pyridine have been determined. The (14)N nuclear quadrupole coupling constants have been obtained for the isotopologues containing this nucleus.

Pure rotational spectrum and model calculations of anisole-ammonia.

The rotational spectra of two isotopologues of the anisole-ammonia molecular complex have been measured with the pulsed-jet Fourier transform microwave technique. The obtained rotational and quadrupole coupling constants provide an unequivocal conformational assignment. The NH(3) group lies out of the plane of the aromatic ring and it is bonded to anisole via three weak, N-H...O, C(Me)-H...N, and N-H...pi contacts.

Molecular recognition of chiral conformers: a rotational study of the dimers of glycidol.

Two homochiral dimers of glycidol, deriving from two different conformers, have been characterized by rotational spectroscopy in a supersonic expansion.

Pure rotational spectra of PbSe and PbTe: potential function, Born-Oppenheimer breakdown, field shift effect and magnetic shielding.

The pure rotational spectra of 41 isotopic species of PbSe and PbTe have been measured in their X 1Sigma+ electronic state with a resonator pulsed-jet Fourier transform microwave spectrometer. The molecules were prepared by laser ablation of suitable target rods and stabilised in supersonic jets of noble gas. Global multi-isotopologue analyses yielded spectroscopic Dunham parameters Y01, Y11, Y21, Y31, Y02, and Y12 for both species, as well as effective Born-Oppenheimer breakdown (BOB) coefficients delta01 for Pb, Se and Te. Unusual large values of the BOB parameters for Pb have been rationalized in terms of finite nuclear size (field shift) effect. A direct fit of the same data sets to an appropriate radial Hamiltonian yielded analytic potential energy functions and BOB radial functions for the X 1Sigma+ electronic state of both PbSe and PbTe. Additionally, the magnetic hyperfine interactions produced by the uneven mass number A nuclei 207Pb, 77Se, 123Te, and 125Te were observed, yielding first determinations of the corresponding nuclear spin-rotation coupling constants.

Multitechnique investigation of conformational features of small molecules: the case of methyl phenyl sulfoxide.

The conformational distribution of methyl phenyl sulfoxide (a molecule representative of a very important class of reagents widely used in asymmetric synthesis) has been studied in two different phases of matter (gas phase and solution) by a comprehensive approach including theoretical calculations, microwave spectroscopy, liquid crystal NMR experiments, and atomistic molecular dynamics computer simulations. The aim was to investigate the combined action of intra- and intermolecular interactions in determining the molecule's conformational equilibrium, upon which important physicochemical properties (inter alia, the chemoselectivity) significantly depend. Basically, the results converge in describing the tendency of the molecule to favor stable conformations governed by intramolecular interactions (in particular, the expected optimization between steric repulsion and conjugation of pi systems). However, significant solvent effects (whose "absolute" magnitude is actually difficult to assess, due to a certain "method-dependence" of the results) have been also detected.

Conformational preferences of chiral molecules: free jet rotational spectrum of 1-phenyl-1-propanol.

The rotational spectra of normal and O-d species of the two most stable conformers of chiral 1-phenyl-1-propanol, obtained by free jet millimetre-wave absorption spectroscopy reveal that both conformers are stabilized by a O-H[dot dot dot]pi interaction, and have the Calpha-Cbeta-bond oriented nearly perpendicular to the plane of the benzene ring. The methyl group is trans with respect to the phenyl group for the most stable conformer (T), while it is gauche with respect to the phenyl group and entgegen with respect to the hydroxyl group for the second most stable conformer (GE). The energy difference (E(GE)-E(T)) was estimated to be 50(50) cm(-1) from relative intensity measurements.

Noncovalent interactions and internal dynamics in dimethoxymethane-water.

The millimeter-wave absorption and Fourier transform microwave spectra of five isotopologues of the 1:1 adduct of dimethoxymethane-water have been measured in supersonic expansions. Each rotational transition appears as a quintuplet, due to the internal rotation of the two methyl groups, which are nonequivalent in the adduct. The water moiety, linked asymmetrically to dimethoxymethane, behaves as a proton donor to one of its oxygen atoms and interferes with the internal rotation of the farther methyl group through a C...HO interaction. From the analysis of the observed splittings, the V(3) barriers to the internal rotation of the two methyl groups have been determined to be 6.83(8) and 6.19(8) kJ mol(-1). The hydrogen bond structural parameters have been determined, the O...HO and C...HO distances being 1.93(1) and 2.78(4) A, respectively.