Rotational spectrum and inversion motions in the neon-dimethyl sulfide complex

The rotational spectra of the (20)Ne and (22)Ne isotopomers of the Ne-dimethyl sulfide (DMS) rare gas dimer have been measured by Fourier transform microwave spectroscopy. MP2/6-311++G(2d,2p) calculations, and the experimental spectroscopic data, suggest a structure of C(s) symmetry in which the Ne atom lies above the heavy atom plane of the DMS (in the sigma(v) plane which bisects the CSC angle). Experimental rotational constants are consistent with a S...Ne distance of 3.943(6) Angstroms and a (cm...S...Ne) angle of 63.2(6) degrees (where cm is the center of mass of DMS). A motion of the Ne atom from one side of the DMS to the other gives rise to inversion splittings of around 3 MHz in the c-type transitions. An ab initio potential energy surface calculation has allowed examination of several possible tunneling pathways, and suggests a barrier of between 20 and 40 cm(-1) for the inversion motion, depending on the tunneling pathway taken by the Ne. Dipole moment measurements are consistent with both the experimental and ab initio structures.     

Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide

Using FTIR and Raman spectroscopy, the formation of halogen bonded complexes of the trifluorohalomethanes CF(3)Cl, CF(3)Br and CF(3)I with dimethyl sulfide (DMS) dissolved in liquid krypton has been investigated. For CF(3)Br and CF(3)I, evidence was found for the formation of C-XS halogen bonded 1:1 complexes. At higher concentrations of CF(3)I weak absorptions due to a 2:1 complex were also observed. Using spectra recorded at temperatures between 118 and 163 K, the complexation enthalpies for the complexes were determined to be -9.5(5) kJ mol(-1) for CF(3)Br·DMS, -17.4(1) kJ mol(-1) for CF(3)I·DMS and -30.8(16) kJ mol(-1) for (CF(3)I·)(2)DMS. The results from the cryospectroscopic study are compared with ab initio calculations at the MP2/aug-cc-pVDZ(-PP) level. Apart from vibrational modes localized in the trifluorohalomethanes and the DMS moieties, for both CF(3)Br and CF(3)I, an additional band, which we assign as the intermolecular stretching mode in the complex, was identified in the infrared and Raman spectra.     

Spectroscopy and structures of copper complexes with ethylenediamine and methyl-substituted derivatives

Copper complexes of ethylenediamine (en), N-methylethylenediamine (meen), N,N-dimethylethylenediamine (dmen), N,N,N'-trimethylethylenediamine (tren), and N,N,N',N'-tetramethylethylenediamine (tmen) are synthesized in laser-vaporization supersonic molecular beams and studied by pulsed-field ionization zero electron kinetic energy (ZEKE) and photoionization efficiency spectroscopies and second-order Moller-Plesset perturbation theory. Precise ionization energies and vibrational frequencies of Cu-en, -meen, and -dmen are measured from the ZEKE spectra, and ionization thresholds of Cu-tren and -tmen are estimated from the photoionization efficiency spectra. The measured vibrational modes span a frequency range of 35-1646 cm(-1) and include metal-ligand stretch and bend, hydrogen-bond stretch, and ligand-based torsion. A number of low-energy structures with Cu binding to one or two nitrogen atoms are predicted for each complex by the ab initio calculations. The combination of the spectroscopic measurements and ab initio calculations has identified a hydrogen-bond-stabilized monodentate structure for the Cu-en complex and bidentate cyclic structures for the methyl-substituted derivatives. The change of the Cu binding from the monodentate to the bidentate mode arises from the competition between copper coordination and hydrogen bonding.     

Molecular structures of the two most stable conformers of free glycine

The equilibrium molecular structures of the two lowest-energy conformers of glycine, Gly-Ip and Gly-IIn, have been characterized by high-level ab initio electronic structure computations, including all-electron cc-pVTZ CCSD(T) geometry optimizations and 6-31G* MP2 quartic force fields, the latter to account for anharmonic zero-point vibrational effects to isotopologic rotational constants. Based on experimentally measured vibrationally averaged effective rotational constant sets of several isotopologues and our ab initio data for structural constraints and zero-point vibrational shifts, least-squares structural refinements were performed to determine improved Born-Oppenheimer equilibrium (r(e)) structures of Gly-Ip and Gly-IIn. Without the ab initio constraints even the extensive set of empirical rotational constants available for 5 and 10 isotopologues of Gly-Ip and Gly-IIn, respectively, cannot satisfactorily fix their molecular structure. Excellent agreement between theory and experiment is found for the rotational constants of both conformers, the rms residual of the final fits being 7.8 and 51.6 kHz for Gly-Ip and Gly-IIn, respectively. High-level ab initio computations with focal point extrapolations determine the barrier to planarity separating Gly-IIp and Gly-IIn to be 20.5 +/- 5.0 cm(-1). The equilibrium torsion angle tau(NCCO) of Gly-IIn, characterizing the deviation of its heavy-atom framework from planarity, is (11 +/- 2) degrees. Nevertheless, in the ground vibrational state the effective structure of Gly-IIn has a plane of symmetry.     

Investigation of the structural units of germanium sulfide and selenide by quantum chemical methods

This article deals with the modeling of the structural units (clusters) of germanium sulfide and germanium selenide glasses by quantum chemical (ab initio Hartree–Fock) methods. Clusters of different sizes were investigated. Geometric parameters and vibrational frequencies of these structural units were calculated. The quantum chemical calculations were followed by normal coordinate analysis. Based on the yielded results, the vibrational spectra of the clusters were simulated. The results for germanium sulfide and germanium selenide were compared. It was concluded that in the spectral regions where germanium sulfide is not applicable for fiber optics, germanium selenide or different germanium sulfide–selenides are suitable to replace it. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Vibrational spectroscopy of the pyridazine cation in the ground state

Vibrational structure of the pyridazine cation in the ground state has been revealed by a vacuum-ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. The adiabatic ionization energy is precisely measured to be 70241 +/- 6 cm(-1) (8.7088 +/- 0.0007 eV). The origin is very weakly observed, while a long progression of the nu9(+) (a1) band of which the fundamental vibrational frequency is 647 cm(-1) is predominantly observed. The nu9(+) (a1) mode progression combined with one quantum of the nu3(+) (a1) band at 1698 cm(-1) is found to be even stronger. Many other weakly observed vibrational features of the pyridazine cation are identified in the vibrational energy of 0-3500 cm(-1). The structural change of pyridazine upon ionization, reflected in the vibrational spectrum obtained by the one-photon direct ionization process, is theoretically predicted by ab initio calculations. Ring distortion including contraction of the N=N bond should be responsible for strong excitations of nu3(+) and nu9(+) modes. Franck-Condon analysis is given for the comparison of the experiment and theory.     

Effect of noncovalent interactions on conformers of the n-butylbenzene monomer studied by mass analyzed threshold ionization spectroscopy and basis-set convergent ab initio computations

Two conformational isomers of the aromatic hydrocarbon n-butylbenzene have been studied using two-color MATI (mass analyzed threshold ionization) spectroscopy to explore the effect of conformation on ionization dynamics. Cationic states of g auche-conformer III and anti- conformers IV were selectively produced by two-color excitation via the respective S 1 origins. Adiabatic ionization potentials of the gauche- and anti-conformations were determined to be 70146 and 69872 +/- 5 cm (-1) respectively. Spectral features and vibrational modes are interpreted with the aid of MP2/cc-pVDZ ab initio calculations, and ionization-induced changes in the molecular conformations are discussed. Complete basis set (CBS) ab initio studies at MP2 level reveal reliable energetics for all four n-butylbenzene conformers observed in earlier two-color REMPI (resonance enhanced multiphoton ionization) spectra. For the S 0 state, the energies of conformer III, IV and V are above conformer I by 130, 289, 73 cm (-1), respectively. Furthermore, the combination of the CBS calculations with the measured REMPI, MATI spectra allowed the determination of the energetics of all four conformers in the S 1 and D 0 states.     

Resonantly enhanced multiphoton ionization and zero kinetic energy photoelectron spectroscopy of 2-indanol conformers

We report studies of a supersonically cooled 2-indanol using two-color resonantly enhanced multiphoton ionization (REMPI) and two-color zero kinetic energy (ZEKE) photoelectron spectroscopy. In the REMPI experiment, we have identified three conformers of 2-indanol and assigned the vibrational structures of the first electronically excited state for the two major conformers. Conformer Ia contains an intramolecular hydrogen bond between the -OH group and the phenyl ring, while conformer IIb has the -OH group in the equatorial position. We have further investigated the vibrational spectroscopy of the cation for the two major conformers using the ZEKE spectroscopy. The two conformers display dramatically different vibrational distributions. The ZEKE spectrum of conformer Ia shows an extensive progression in the puckering mode of the five member ring, indicating a significant geometry change upon ionization. The ZEKE spectra of conformer IIb are dominated by single vibronic transitions, and the intensity of the ZEKE signal is much stronger than that of conformer Ia. These results indicate an invariance of the molecular frame during ionization for conformer IIb. We have performed ab initio and density functional theory calculations to obtain potential energy surfaces along the dihedral angle involving the -OH group for all three electronic states. In addition, we have also calculated the vibrational distribution of the ZEKE spectrum for the puckering mode of the five member ring. Not only the vibrational frequencies but also the intensity distributions for both conformers have been reproduced satisfactorily. The adiabatic ionization energies have been determined to be 68 593+/-5 cm(-1) for conformer Ia and 68 981+/-5 cm(-1) for conformer IIb.     

Quantum chemical study on the abstraction reaction of alkylidenegermylene with oxirane and thiirane

The mechanisms of theion reaction of alkylidenegermylene with oxirane and thiirane have been characterized detail in using density functional theory, as well as ab initio method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies were calculated by CCSD(T)/6-311G(d)//B3LYP/6-311G(d,p) method for the involved conformations. The results show that the reaction pathways for both reactions consist of two ways: (1) the reactants can yield bent products (P1; P4) by syn-isomers; (2) the reactants can also yield three-membered products (P2; P5) by anti-isomers, which then further react with oxirane and thiirane to form the ultimate products (P3-1, P3-2; P6). Furthermore, a comparison with alkylidenecarbene, oxirane, and thiirane was done.     

Ab initio study of the structure, bonding, vibrational spectra, and energetics of XBS+ (where X=H, F, and Cl)

High level ab initio electronic structure calculations at the CCSD(T) level with augmented correlation-consistent basis set extrapolated to complete basis set limit have been performed on XBS and XBS+ for X=H, F, and Cl. The geometries have been optimized up through the aug-cc-pV5Z level and the vibrational frequencies have been calculated with the aug-cc-pVQZ basis sets. Analysis of the bonding in XBS and XBS+ using natural bond orbital analysis shows that the BS bond in XBS is a triple bond, while in XBS+ it is a double bond. The energetic properties of XBS cation and its first excited state are reported. The calculated adiabatic ionization potential is 11.11+/-0.01 eV as compared to the experimental value of 11.11+/-0.03 eV for HBS. The adiabatic ionization potentials for FBS and CIBS are 10.89+/-0.01 and 10.57+/-0.01 eV, respectively.     

Vacuum ultraviolet laser pulsed field ionization-photoelectron study of allyl radical CH2CHCH2

The pulsed field ionization-photoelectron (PFI-PE) spectrum of allyl radical CH2CHCH2 (C3H5) in the energy range of 65 200-66 600 cm-1 has been measured using vacuum ultraviolet laser. Based on the simulation of the rotational structures resolved in the vibrational PFI-PE bands of C3H5+(X 1A1;0(0+) and nu7+=1), the ionization energies (IEs) of C3H5(X 2A2;0(0)) to form C3H5+(X 1A1;0(0+) and nu7+=1) are determined to be 65 584.6+/-2.0 cm-1 (8.131 46+/-0.000 25 eV) and 66 020.9+/-2.0 cm-1 (8.185 56+/-0.000 25 eV), respectively, where nu7+(a1) is the symmetric C-C-C bending mode of C3H5+(X 1A1). These values are compared to IE(C3H5) values obtained in previous experimental and high-level ab initio quantum theoretical studies.     

Theoretical studies on the potential energy surface and rovibrational states for the electronic ground state of carbonyl sulfide

A potential energy surface for the electronic ground state of carbonyl sulfide was optimized by using a self-consistent field-configuration interaction method and involving the recent observed vibrational band origins up to 8000 cm⁻¹ for the Σ state. The root mean square error for this refinement was found to be 0.27 cm⁻¹. The calculated quartic force constants from the refined potential are very close to the recent high level ab initio calculations. The vibrational energy levels for the Π and Δ states and for some isotopomers of carbonyl sulfide molecule were calculated to test the refined potential. The calculated energy levels are in good agreement with the experimental values.     

A new ab initio ground-state dipole moment surface for the water molecule

A valence-only (V) dipole moment surface (DMS) has been computed for water at the internally contracted multireference configuration interaction level using the extended atom-centered correlation-consistent Gaussian basis set aug-cc-pV6Z. Small corrections to these dipole values, resulting from core correlation (C) and relativistic (R) effects, have also been computed and added to the V surface. The resulting DMS surface is hence called CVR. Interestingly, the C and R corrections cancel out each other almost completely over the whole grid of points investigated. The ground-state CVR dipole of H(2) (16)O is 1.8676 D. This value compares well with the best ab initio one determined in this study, 1.8539+/-0.0013 D, which in turn agrees well with the measured ground-state dipole moment of water, 1.8546(6) D. Line intensities computed with the help of the CVR DMS shows that the present DMS is highly similar to though slightly more accurate than the best previous DMS of water determined by Schwenke and Partridge [J. Chem. Phys. 113, 16 (2000)]. The influence of the precision of the rovibrational wave functions computed using different potential energy surfaces (PESs) has been investigated and proved to be small, due mostly to the small discrepancies between the best ab initio and empirical PESs of water. Several different measures to test the DMS of water are advanced. The seemingly most sensitive measure is the comparison between the ab initio line intensities and those measured by ultralong pathlength methods which are sensitive to very weak transitions.     

Resonantly enhanced two photon ionization and zero kinetic energy spectroscopy of jet-cooled 4-aminopyridine

We report studies of supersonically cooled 4-aminopyridine (4-AP) using two-color resonantly enhanced multiphoton ionization (REMPI) and two-color zero kinetic energy (ZEKE) photoelectron spectroscopy. With the aid of ab initio and density functional calculations, vibrational modes of the first electronically excited state (S1) of the neutral species and those of the cation have been assigned, and the adiabatic ionization potential has been determined to be 62291+/-6 cm(-1). The REMPI spectrum of the S1 state is dominated by ring deformation modes and the inversion mode of the amino group, while the ZEKE spectra demonstrate a strong propensity of Deltav=0, where v is the vibrational quantum number of the intermediate vibronic state from S1. In addition, the ZEKE spectra obtained via different vibrational levels of the S1 state contain four common features, corresponding to the activation of four different vibrational modes of the cation. These observations are explained in terms of the structural changes from the ground state to S1 and further to the cation. The vibrational mode distributions in both the REMPI and the ZEKE spectra, the excitation energy of the S1 state, and the ionization potential of 4-AP, are remarkably similar to those of aniline, suggesting that the electronic activity is centered on the ring.     

Chemical insights from high-resolution X-ray photoelectron spectroscopy and ab initio theory: propyne, trifluoropropyne, and ethynylsulfur pentafluoride.

High-resolution carbon 1s photoelectron spectroscopy of propyne (HC triple bond CCH3) shows a spectrum in which the contributions from the three chemically inequivalent carbons are clearly resolved and marked by distinct vibrational structure. This structure is well accounted for by ab initio theory. For 3,3,3-trifluoropropyne (HC triple bond CCF3) and ethynylsulfur pentafluoride (HC triple bond CSF5), the ethynyl carbons show only a broad structure and have energies that differ only slightly from one another. The core-ionization energies can be qualitatively understood in terms of conventional resonance structures; the vibrational broadening for the fluorinated compounds can be understood in terms of the effects of the electronegative fluorines on the charge distribution. Combining the experimental results with gas-phase acidities and with ab initio calculations provides insights into the effects of initial-state charge distribution and final-state charge redistribution on ionization energies and acidities. In particular, these considerations make it possible to understand the apparent paradox that SF5 and CF3 have much larger electronegativity effects on acidity than they have on carbon 1s ionization energies.     

DFT and ab initio calculations on two reactions between hydrogen atoms and the fire suppressants 2-H heptafluoropropane and CF3Br

Reaction enthalpies and barrier heights of the reactions CF3Br+H-->CF3+HBr {reaction (1)} and CF3CHFCF3+H-->CF3CFCF3+H2 {reaction (2)} have been calculated at the near state-of-the-art ab initio level, and also by employing the B3LYP, BH&HLYP, BB1K, MPW1K, MPWB1K and TPSS1KCIS functionals. In addition, the integrated molecular orbital+molecular orbital (IMOMO) method has been used to study reaction (2). The ab initio benchmark values of the reaction enthalpy (298 K) and barrier height (0 K) of reaction (2) are reported for the first time {-(0.7+/-0.7) and 13.3+/-0.5 kcal/mole respectively}. When density functional theory (DFT) results are compared with ab initio benchmarks for both reactions (1) and (2), the MPWB1K functional is found to have the best performance of the six functionals used. The IMOMO method with the RCCSD/aug-cc-pVTZ and/or RCCSD(T)/aug-cc-pVTZ levels, as the high levels of calculation on the model system, gives reaction enthalpies and barrier heights of reaction (2), which agree with ab initio benchmark values to within 1 kcal/mole. Computed key geometrical parameters and imaginary vibrational frequencies of the transition state structures of reactions (1) and (2) obtained at different levels of calculation are compared. The magnitudes of the computed imaginary vibrational frequencies of the transition states of both reactions considered are found to be very sensitive to the levels of calculation used to obtain them. The heat of formation (298 K) of CF3CFCF3 calculated at the near state-of-the-art level has a value of -(318+/-3) kcal/mole.     

Mass analyzed threshold ionization spectroscopy of o-, m-, and p-dichlorobenzenes. Influence of the chlorine position on vibrational spectra and ionization energy

For the first time, vibrational spectra of the 35Cl2 and 35Cl37Cl isotopomers of o-, m-, and p-dichlorobenzene cations in the electronic ground state have been measured via S1 intermediate states by mass analyzed threshold ionization (MATI) spectroscopy. Additionally, ab initio calculations at DFT (density functional theory), CIS (configuration interaction singles), and CASSCF (complete active space self-consistent field) levels of theory have been conducted to compare experimental findings with theory. From the MATI spectra, adiabatic ionization energies of the ortho, meta, and para isomers have been determined to be the same for each pair of investigated isotopomers to 73,237 +/- 6, 72,191 +/- 6, and 73,776 +/- 6 cm(-1), respectively. Several vibrational modes, including fundamentals, combinations, and progressions have been assigned by comparing the experimental and theoretical results. The appearance of overtone progressions involving the 7a mode could be explained by a geometry change of all three isomers during ionization in the direction of this mode by retraining the symmetry of the molecules. Although the general spectral features of the investigated isotopomers are similar, frequencies of some vibrations are slightly different up to a few wavenumbers depending on the involvement of the chlorine atoms in the molecular motion.     

Zero kinetic energy photoelectron spectroscopy of tetracene using laser desorption for vaporization

Far infrared (FIR) spectroscopy of polycyclic aromatic hydrocarbons is of particular interest to astrophysics since vibrational modes in this range are representative of the molecular size and shape. This information is hence important for identification of chemical compositions and for modeling of the IR spectrum observed in the outer space. In this work, we report neutral and cation FIR spectroscopy of tetracene vaporized from a laser desorption source. Results from two-color resonantly enhanced multiphoton ionization and two-color zero kinetic energy photoelectron spectroscopy will be presented. Several skeletal vibrational modes of the first electronically excited state of the neutral species and those of the cation are assigned, with the aid of ab initio and density functional calculations. The adiabatic ionization potential is determined to be 55 918 +/- 7 cm(-1). Interestingly, all observed vibrational modes can be rationalized based on a simple Huckle calculation, i.e., by observing the addition or elimination of nodal planes due to electronic excitation and/or ionization. Limited by the Franck-Condon principle and the rigidity of the molecular frame of tetracene, only IR forbidden modes are observed in this work.     

H2S·HOH or H2O·HSH, which is more stable in the water-hydrogen sulfide complex?

High-level ab initio calculations are carried out to study the relative stability of the two hydrogen bonded structures of water-hydrogen sulfide complex, one with water as the proton donor (A) and the other with hydrogen sulfide as the proton donor (B). The results show that structure A is considerably more stable than B at the correlated level, which is in contrast with previous results obtained from Hartree-Fock calculations.     

Ab initio potential energy and dipole moment surfaces of (H2O)2

A full-dimensional ab initio potential energy surface (PES) and dipole moment surface (DMS) are reported for the water dimer, (H2O)2. The CCSD(T)-PES is a very precise fit to 19,805 ab initio energies obtained with the coupled-cluster (CCSD(T)) method, using an aug-cc-pVTZ basis. The standard counterpoise correction was applied to approximately eliminate basis set superposition errors. The fit is based on an approach that incorporates the permutational symmetry of identical atoms [Huang, X.; Braams, B.; Bowman, J. M. J. Chem.Phys. 2005, 122, 044308]. The DMS is a fit to the dipole moment obtained with M?ller-Plesset (MP2) theory, using an aug-cc-pVTZ basis. The PES has an RMS fitting error of 31 cm(-1) for energies below 20,000 cm(-1), relative to the global minimum. This surface can describe various internal floppy motions, including various monomer inversions, and isomerization pathways. Ten characteristic stationary points have been located on the surface, four of which are transition structures and the rest are higher order saddle points. Their geometrical and vibrational properties are presented and compared with available previous theoretical work. The CCSD(T)-PES and MP2-DMS dissociate correctly (and symmetrically) to two H2O monomers, with D(e) = 1665.7 cm(-1) (19.93 kJ/mol). Accurate quantum calculations of the zero-point energy of the dimer (using diffusion Monte Carlo) and the monomers (using a vibrational configuration interaction approach) are reported, and these together with D(e) give a value of D0 of 1042 cm(-1) (12.44 kJ/mol). A best estimated value is 1130 cm(-1) (13.5 kJ/mol).