The roaming atom pathway in formaldehyde decomposition

We present a detailed experimental and theoretical investigation of formaldehyde photodissociation to H(2) and CO following excitation to the 2(1)4(1) and 2(1)4(3) transitions in S(1). The CO velocity distributions were obtained using dc slice imaging of single CO rotational states (v=0, j(CO)=5-45). These high-resolution measurements reveal the correlated internal state distribution in the H(2) cofragments. The results show that rotationally hot CO (j(CO) approximately 45) is produced in conjunction with vibrationally "cold" H(2) fragments (v=0-5): these products are formed through the well-known skewed transition state and described in detail in the accompanying paper. After excitation of formaldehyde above the threshold for the radical channel (H(2)CO-->H+HCO) we also find formation of rotationally cold CO (j(CO)=5-28) correlated to highly vibrationally excited H(2) (v=6-8). These products are formed through a novel mechanism that involves near dissociation followed by intramolecular H abstraction [D. Townsend et al., Science 306, 1158 (2004)], and that avoids the region of the transition state entirely. The dynamics of this "roaming" mechanism are the focus of this paper. The correlations between the vibrational states of H(2) and rotational states of CO formed following excitation on the 2(1)4(3) transition allow us to determine the relative contribution to molecular products from the roaming atom channel versus the conventional molecular channel.     

Potassium-intercalated H(2)Pc films: Alkali-induced electronic and geometrical modifications

X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In addition, the comparison of valence band photoemission spectra with the density functional theory calculations of the density of states of the H(2)Pc(-) anion indicates a filling of the formerly lowest unoccupied molecular orbital by charge transfer from the alkali. This is further confirmed by x-ray absorption spectroscopy (XAS) studies, which show a decreased density of unoccupied states. XAS measurements in different experimental geometries reveal that the molecules in the pristine film are standing upright on the surface or are only slightly tilted away from the surface normal but upon K intercalation, the molecular orientation is changed in that the tilt angle of the molecules increases.     

Valence and dipole-bound anions of the most stable tautomers of guanine

Anionic states of guanine, which is the only nucleic acid base of which the anions have not yet been studied in either photoelectron spectroscopic (PES) or Rydberg electron transfer (RET) experiments, have been characterized for the four most stable tautomers of neutral guanine using a broad spectrum of electronic structure methods from the density functional theory, with the B3LYP exchange-correlation functional, to the coupled-cluster method, with single, double, and perturbative triple excitations. Both valence and dipole-bound anionic states were addressed. We identified some of the difficulties facing future PES or RET experiments on the anion of guanine. Even if guanine is successfully transferred to the gas phase without thermal decomposition, it is critical to have the canonical amino-oxo (G) and both amino-hydroxy (GH and GHN7H) tautomers in the beam, not only the most stable, a noncanonical, amino-oxo tautomer (GN7H), as the latter does not support an adiabatically bound anionic state. We also suggested a scheme for enrichment of gas-phase guanine with the canonical tautomer, which is not the most stable in the gas phase, but which is of main interest due to its biological relevance. The tautomers G, GN7H, and GHN7H support vertically bound valence anionic states with the CCSD(T) value of vertical detachment energy of +0.58, +0.21, and +0.39 eV, respectively. These anionic states are, however, adiabatically unbound and thus metastable. The vertical electronic stability of these valence anionic states is accompanied by serious "buckling" of the molecular skeleton. The G and GHN7H tautomers support dipole-bound states with the CCSD(T) values of adiabatic electron affinity of 65 and 36 meV, respectively. A contribution from higher-than-second-order correlation terms represents, respectively, 48 and 68% of the total vertical electron detachment energy determined at the CCSD(T) level.     

Elucidating connectivity and metal-binding structures of unlabeled paramagnetic complexes by 13C and 1H solid-state NMR under fast magic angle spinning

Characterizing paramagnetic complexes in solids is an essential step toward understanding their molecular functions. However, methodologies to characterize chemical and electronic structures of paramagnetic systems at the molecular level have been notably limited, particularly for noncrystalline solids. We present an approach to obtain connectivities of chemical groups and metal-binding structures for unlabeled paramagnetic complexes by 13C and 1H high-resolution solid-state NMR (SSNMR) using very fast magic angle spinning (VFMAS, spinning speed >or=20 kHz). It is experimentally shown for unlabeled Cu(II)(Ala-Thr) that 2D 13C/1H correlation SSNMR under VFMAS provides the connectivity of chemical groups and assignments for the characterization of unlabeled paramagnetic systems in solids. We demonstrate that on the basis of the assignments provided by the VFMAS approach multiple 13C-metal distances can be simultaneously elucidated by a combination of measurements of 13C anisotropic hyperfine shifts and 13C T1 relaxation due to hyperfine interactions for this peptide-Cu(II) complex. It is also shown that an analysis of 1H anisotropic hyperfine shifts allows for the determination of electron-spin states in Fe(III)-chloroprotoporphyin-IX in solid states.     

Vibrational analysis of the H5O2+ infrared spectrum using molecular and driven molecular dynamics

Standard molecular and driven molecular dynamics are used to analyze prominent spectral features in the H5O2+ infrared spectrum. In the driven method, the molecular Hamiltonian is augmented with a time-dependent term, mu x epsilon(0) sin(omegat), where mu is the dipole moment of H5O2+, epsilon0 is the electric field, and omega is the frequency. The magnitude of the electric field determines whether the driving is mild (the harmonic limit) or strong (anharmonic motion and mode coupling). We analyze the spectrum in the wavenumber range from 600 to 1900 cm(-1), where recent experimental measurements are available for H5O2+. On the basis of the simulations, we have assigned the broad feature around 1000 cm(-1) to the proton transfer coupled with the torsion motion. Intense absorption near 1780 cm(-1) is assigned to the H2O monomer bend coupled with proton transfer.     

Resolution and structural transitions of elongated states of ubiquitin

Electrospray ionization, combined with two-dimensional ion mobility spectrometry and mass spectrometry, is used to produce, select, and activate distributions of elongated ions, [M + 11H]11+ to [M + 13H]13+, of ubiquitin. The analysis makes it possible to examine state-to-state transitions for structural types, and transition diagrams associated with the efficiencies of structural changes are presented. The +11 and +12 charge states can form four resolvable states while only one state is formed for [M + 13H]13+. Some conformations, which appear to belong to the same family based on mobility analysis of different charge states, undergo similar transitions, others do not. Activation of ions that exist in low-abundance conformations, having mobilities that fall in between sharp peaks associated with higher abundances species, shows that the low-abundance forms undergo efficient (approximately 90 to 100%) conversion into states associated with well-defined peaks. This efficiency is significantly higher than the approximately 10 to 60% efficiency of transitions of structures associated with well-defined peaks. The formation of sharp features from a range of low-intensity species with different cross sections indicates that large regions of conformation space must be unfavorable or inaccessible in the gas phase. These results are compared with several previous IMS measurements of this system as well as information about gas-phase structure provided by other techniques.     

Experimental and theoretical investigation of the decomposition of lithiated hydroxyl side-chain amino acids

Lithium cation complexes with serine (Ser) and threonine (Thr) are collisionally activated with xenon in a guided ion beam tandem mass spectrometer and are observed to exhibit a variety of decomposition pathways in addition to a loss of the intact ligand. Prominent pathways include a loss of H2O, CO2, and aldehydes (XCHO where X=H for Ser and CH3 for Thr). Quantum chemical calculations at the B3LYP/6-311+G(d,p) level are used to explore the reaction mechanisms for these processes in detail. Complete potential energy surfaces for all three processes are elucidated, including all intermediates and transition states. Theoretical molecular parameters for the rate-limiting transition states are then used to analyze the threshold energies in the experimental data, providing experimental measurements of the energies of these transition states. These experimental energies are compared with single-point energies calculated at three different levels, B3LYP, B3P86, and MP2(full), using the 6-311+G(2d,2p) basis set with geometries and zero-point energies calculated at the B3LYP/6-311+G(d,p) level. Good agreement between experiment and theory (especially MP2(full)) suggests that the reaction mechanisms have been reasonably elucidated.     

Theoretical Study on Mechanism of C5H7·+O2 Reaction

The potential energy surface (PES) for the reaction of E,E-pentadienyl with molecular oxygen was theoretically studied at the G3B3//B3LYP/6-311G(d,p) level of theory. The first step of the reaction was found to be the direct adduction of molecular O2 on either the C1 or the C3 atoms of E,E-pentadienyl, forming two C5H7O2· isomers. These two C5H7O2· isomers undergo a series of isomerization processes through either the hydrogen-transfer or cyclization pathway. In the final step, the hydrogen-transferred and cyclized isomers decompose into unsaturated aldehydes, unsaturated ketones, and hydroxyl radicals. Involves 20 stable species and 14 transition states, and the energies and structures of all reactants, products and transition states were calculated. Based on the calculated barriers and heats of formation, the authors suggest that the C2H3O·+C3H4O formation channel is the dominant channel for the C5H7·+O2 reaction. The possible existence of C5H7O2· radicals as long lifetime intermediates is also proposed, which is consistent with the recent photoionization mass spectrometric experiments by Zils et al.     

Non-Born-Oppenheimer variational calculations of HT+ bound states with zero angular momentum

We report fully nonadiabatic calculations of all rotationless bound states of HT+ molecular ion (t+p+e-) carried out in the framework of the variational method. We show that, in all the states, except the two highest ones, the bond in the system can be described as covalent. In the highest two states the bond becomes essentially ionic and HT+ can be described as a T+H+ complex. The wave function of the system was expanded in terms of spherically symmetric, explicitly correlated Gaussian functions with preexponential multipliers consisting of powers of the internuclear distance. Apart from the total energies of the states, we have calculated the expectation values of the t-p, t-e, and p-e interparticle distances, their squares, and the nucleus-nucleus correlation functions.     

The energy landscape of unsolvated peptides: the role of context in the stability of alanine/glycine helices

Ion mobility measurements have been used to examine the conformations present for unsolvated Ac-(AG)(7)A+H(+) and (AG)(7)A+H(+) peptides (Ac = acetyl, A = alanine, and G = glycine) over a broad temperature range (100-410 K). The results are compared to those recently reported for Ac-A(4)G(7)A(4)+H(+) and A(4)G(7)A(4)+H(+), which have the same compositions but different sequences. Ac-(AG)(7)A+H(+) shows less conformational diversity than Ac-A(4)G(7)A(4)+H(+); it is much less helical than Ac-A(4)G(7)A(4)+H(+) at the upper end of the temperature range studied, and at low temperatures, one of the two Ac-A(4)G(7)A(4)+H(+) features assigned to helical conformations is missing for Ac-(AG)(7)A+H(+). Molecular dynamics simulations suggest that the different conformational preferences are not due to differences in the stabilities of the helical states, but differences in the nonhelical states: it appears that Ac-(AG)(7)A+H(+) is more flexible and able to adopt lower energy globular conformations (compact random looking three-dimensional structures) than Ac-A(4)G(7)A(4)+H(+). The helix to globule transition that occurs for Ac-(AG)(7)A+H(+) at around 250-350 K is not a direct (two-state) process, but a creeping transition that takes place through at least one and probably several intermediates.     

High-Resolution Infrared-Vacuum Ultraviolet Photoion and Pulsed Field Ionization-Photoelectron Methods for Spectroscopic Studies of Neutrals and Cations

We show that by scanning the frequency of a single mode infrared (IR) optical parametric oscillator (IR-OPO) laser to excite the molecular species of interest and fixing the frequency of a vacuum ultraviolet (VUV) laser to photoionize the IR excited species, high-resolution IR spectra of polyatomic neutrals can be obtained with high sensitivity. The fact that this IR-VUV-photoion (IR-VUV-PI) method is based on VUV photoionization probe, and thus, allows the identification of the neutral IR absorber, makes it applicable for IR spectroscopy measurements of isotopemers, radicals, and clusters, which usually exist as impure samples. The highly resolved IR-VUV-PI measurements achieved using the single mode IR-OPO laser have made possible the selection of single rovibrational states of CH3X (X=Br and I), C2H4, and C3H4 for VUV-pulsed field ionization-photoelectron (VUV-PFI-PE) measurements, resulting in rovibrationally resolved photoelectron spectra for these polyatomic molecules. These experiments show that the signal-to-noise ratios of the IR-VUV-PI and IR-VUV-PFI-PE spectra obtained by employing the high-resolution IR-OPO laser are significantly higher than those observed in previous IR-VUV-PI and IR-VUV-PFI-PE studies using a low-resolution IR-OPO laser. Further improvement in sensitivity of IR-VUV-PI and IR-VUV-PFI-PE measurements by using the collinear arrangement of IR-VUV lasers and molecular beam is discussed.     

Elastic and charge transfer processes in H+ + CO collisions

Proton and hydrogen atom time-of-flight spectra in collision energy range of E(trans) = 9.5-30 eV show that the endoergic charge transfer process in the H+ + CO system is almost an order of magnitude less probable than the elastic scattering [G. Niedner-Schatteburg and J. P. Toennies, Adv. Chem. Phys. LXXXII, 553 (1992)]. Ab initio computations at the multireference configuration interaction level have been performed to obtain the ground- and several low-lying excited electronic state potential energy curves in three different molecular orientations namely, H+ approaching the O-end and the C-end (collinear), and H+ approaching the CO molecule in perpendicular configuration with fixed CO internuclear distance. Nonadiabatic coupling terms between the ground electronic state (H+ + CO) and the three low-lying excited electronic states (H + CO+) have been computed and the corresponding diabatic potentials have been obtained. A time-dependent wavepacket dynamics study is modeled first involving only the ground and the first excited states and then involving the ground and the three lowest excited states at the collision energy of 9.5 eV. The overall charge transfer probability have been found to be approximately 20%-30% which is in qualitative agreement with the experimental findings.     

Rovibrationally selected and resolved state-to-state photoionization of ethylene using the infrared-vacuum ultraviolet pulsed field ionization-photoelectron method

By preparing ethylene [C2H4(X1Ag)] in selected rotational levels of the nu11(b1u), nu2+nu12(b1u), or nu9(b2u) vibrational state with infrared (IR) laser photoexcitation prior to vacuum ultraviolet (VUV) laser photoionization, we have recorded rotationally resolved pulsed field ionization-photoelectron (PFI-PE) spectra for C2H4+(X2B3u) in the energy region of 0-3000 cm(-1) above the ionization energy (IE) of C2H4(X1Ag). Here, nu2(ag), nu9(b2u), nu11(b1u), and nu12(b1u) represent the C-C stretching, CH2 stretching, CH2 stretching, and CH2 bending modes of C2H4(X1Ag), respectively. The fully rovibrationally resolved spectra have allowed unambiguous symmetry assignments of the observed vibrational bands, which in turn have provided valuable information on the photoionization dynamics of C2H4. The IR-VUV photoionization of C2H4(X1Ag) via the nu11(b1u) or nu2+nu12(b1u) vibrational states is found to predominantly produce vibrational states of C2H4+(X2B3u) with b1u symmetry, which cannot be observed in single-photon VUV-PFI-PE measurements of C2H4(X1Ag). The analysis of the observed IR-VUV-PFI-PE bands has provided the IE(C2H4) = 84,790.2(2) cm(-1) and accurate vibrational frequencies for the nu4+(au)[84.1(2) cm(-1)], nu12+(b1u)[1411.7(2) cm(-1)], nu4+ +nu12+(b1g)[1482.5(2) cm(-1)], nu2+(ag)[1488.3(2) cm(-1)], nu2+ + nu4+(au)[1559.2(2) cm(-1)], 2nu4+ + nu12 +(b1u)[1848.5(2) cm(-1)], 4nu4+ + nu12 +(b1u)[2558.8(2) cm(-1)], nu2+ + nu12 +(b1u)[2872.7(2) cm(-1)], and nu11+(b1u)[2978.7(2) cm(-1)] vibrational states of C2H4+(X2B3u), where nu4+ is the ion torsional state. The IE(C2H4) and the nu4+(au), nu2+(ag), and nu2+ + nu4+ (au) frequencies are in excellent accord with those obtained in previous single-photon VUV-PFI-PE measurements. The other ion vibrational frequencies represent new experimental determinations. We have also performed high-level ab initio anharmonic vibrational frequency calculations for C2H4(X1Ag) and C2H4+(X2B3u) at the CCSD(T)/aug-cc-pVQZ level for guidance in the assignment of the IR-VUV-PFI-PE spectra. All theoretical vibrational frequencies for the neutral and ion, except the ion torsional frequency, are found to agree with experimental vibrational frequencies to better than 1%.     

Crossed beam studies of the reactions of atomic oxygen in the ground 3P and first electronically excited 1D states with hydrogen sulfide

The reactions of both ground, (3)P, and electronically excited, (1)D, oxygen atoms with hydrogen sulfide, H(2)S, have been investigated by means of the crossed molecular beams method with mass spectrometric detection at different collision energies. Amongst the possible reaction channels those leading to HSO+H for the O((3)P) reaction and to HSO/HOS+H and SO+H(2) for the O((1)D) reaction have been identified and investigated. The dynamics of the channels leading to HSO/HOS+H are elucidated for the reactions of both states and the trend with increasing the collision energy analyzed. Noteworthily, the formation of SO+H(2) products appears to be an open channel for the O((1)D) reaction, at least for the highest collision energy investigated (11.8 kcal/mol). Finally, the recent experimental and theoretical estimates of the enthalpy of formation of the HSO radical have been critically analyzed to evaluate their conformity with the present experimental data.     

Single and multiple photoionisation of H2S by 40-250 eV photons

Multi-electron coincidence measurements on photoionisation of H(2)S have been carried out at photon energies from 40 to 250 eV. They quantify molecular field effects on the Auger process in detail and are in good agreement with the existing theory. Spectra of core-valence double ionisation of H(2)S are presented and partially analysed. Auger decays from the core-valence states produce triply charged product spectra with unexplained and surprising intensity distributions. Triple ionisation by the double Auger process from 2p hole states shows little effect of the molecular field splitting, but includes a substantial contribution from cascade processes, some involving dissociation in intermediate states. The onset of triple ionisation at the molecular geometry is determined as 61 ± 0.5 eV.     

Time dependent quantum dynamics study of the Ne + H2+(v=0-4)-->NeH+ + H proton transfer reaction

The Ne + H2+-->NeH+ + H proton transfer reaction was studied using the time dependent real wave packet quantum dynamics method at the helicity decoupling level, considering the H2+ molecular ion in the (v=0-4, j=0) vibrorotational states and a wide collision energy interval. The calculated reaction probabilities and reaction cross sections were in a rather good agreement with reanalyzed previous exact quantum dynamics results, where a much smaller collision energy interval was considered. Also, a quite good agreement with experimental data was found. These results suggested the adequacy of the approach used here to describe this and related systems.     

Theoretical study of the reaction of ethane with oxygen molecules in the ground triplet and singlet delta States

Quantum chemical calculations are carried out to study the reaction of ethane with molecular oxygen in the ground triplet and singlet delta states. Transition states, intermediates, and possible products of the reaction on the triplet and singlet potential energy surfaces are identified on the basis of the coupled-cluster method. The basis set dependence of coupled-cluster energy values is estimated by the second-order perturbation theory. The values of energy barriers are also refined by using the compound CBS-Q and G3 techniques. It was found that the C(2)H(6) + O(2)(X(3)Σ(g)(-)) reaction leads to the formation of C(2)H(5) and HO(2) products, whereas the C(2)H(6) + O(2)(a(1)Δ(g)) process produces C(2)H(4) and H(2)O(2) molecules. The appropriate rate constants of these reaction paths are estimated on the basis of variational and nonvariational transition-state theories assuming tunneling and possible nonadiabatic transitions in the temperature range 500-4000 K. The calculations showed that the rate constant of the C(2)H(6) + O(2)(a(1)Δ(g)) reaction path is much greater than that of the C(2)H(6) + O(2)(X(3)Σ(g)(-)) one. At the same time, the singlet and triplet potential surface intersection is detected that leads to the appearance of the nonadiabatic quenching channel O(2)(a(1)Δ(g)) + C(2)H(6) → O(2)(X (3)Σ(g)(-)) + C(2)H(6). The rate constant of this process is estimated with the use of the Landau-Zener model. It is demonstrated that, in the case of the existence of thermal equilibrium in the distribution of molecules over the electronic states, at low temperatures (T < 1200 K) the main products of the reaction of C(2)H(6) with O(2) are C(2)H(4) and H(2)O(2), rather than C(2)H(5) and HO(2). At higher temperature (T > 1200 K) the situation is inverted.     

Sequential reduction of high hydride count octahedral rhodium clusters [Rh6(PR3)6H12][BArF4]2: redox-switchable hydrogen storage

Cyclic voltammetry on the octahedral rhodium clusters with 12 bridging hydride ligands, [Rh6(PR3)6H12][BArF4]2 (R = Cy Cy-[H12]2+, R = iPr iPr-[H12]2+; [BArF4]- = [B{C6H3(CF3)2}4]-) reveals four potentially accessible redox states: [Rh6(PR3)6H12]0/1+/2+/3+. Chemical oxidation did not produce stable species, but reduction of Cy-[H12]2+ using Cr(eta6-C6H6)2 resulted in the isolation of Cy-[H12]+. X-ray crystallography and electrospray mass spectrometry (ESI-MS) show this to be a monocation, while EPR and NMR measurements confirm that it is a monoradical, S = 1/2, species. Consideration of the electron population of the frontier molecular orbitals is fully consistent with this assignment. A further reduction is mediated by Co(eta5-C5H5)2. In this case the cleanest reduction was observed with the tri-isopropyl phosphine cluster, to afford neutral iPr-[H12]. X-ray crystallography confirms this to be neutral, while NMR and magnetic measurements (SQUID) indicate an S =1 paramagnetic ground state. The clusters Cy-[H12]+ and iPr-[H12] both take up H2 to afford Cy-[H14]+ and iPr-[H14], respectively, which have been characterized by ESI-MS, NMR spectroscopy, and UV-vis spectroscopy. Inspection of the frontier molecular orbitals of S = 1 iPr-[H12] suggest that addition of H2 should form a diamagnetic species, and this is the case. The possibility of "spin blocking" in this H2 uptake is also discussed. Electrochemical investigations on the previously reported Cy-[H16]2+ [J. Am. Chem. Soc. 2006, 128, 6247] show an irreversible loss of H2 on reduction, presumably from an unstable Cy-[H16]+ species. This then forms Cy-[H12]2+ on oxidation which can be recharged with H2 to form Cy-[H16]2+. We show that this loss of H2 is kinetically fast (on the millisecond time scale). Loss of H2 upon reduction has also been followed using chemical reductants and ESI-MS. This facile, reusable gain and loss of 2 equiv of H2 using a simple one-electron redox switch represents a new method of hydrogen storage. Although the overall storage capacity is very low (0.1%) the attractive conditions of room temperature and pressure, actuation by the addition of a single electron, and rapid desorption kinetics make this process of interest for future H2 storage applications.     

Study of ab initio molecular data for inelastic and reactive collisions involving the H3+ quasimolecule

The lowest two ab initio potential energy surfaces (PES), and the corresponding nonadiabatic couplings between them, have been obtained for the H3+ system; the molecular data are compared to those calculated with the diatomic in molecules (DIM) method. The form of the couplings is discussed in terms of the topology of the molecular structure of the triatomic. The method of Baer is employed to generate "diabatic" states and the residual nonadiabatic couplings are calculated. The ab initio results for these are markedly different from the corresponding DIM data, and show the need to consider the third PES.     

Stereodynamics of the Ca + HCl → CaCl + H molecular reaction imposed by the rotational-excited states of HCl

The effects of the initial rotational-excited states of the HCl molecule on the stereodynamics properties of the Ca + HCl molecular reaction are investigated using the quasiclassical trajectory theory and the analytical potential energy surface. The orientation and alignment behaviors for the rotational angular momentum of the product, along with the generalized differential cross section (PDDCS)-dependent polarization, are calculated to explore the stereodynamics properties. The initial rotational-excited states of the HCl molecule impose a remarkable effect on the vector correlation distributions, regardless of the orientation, alignment, or PDDCS. The forward, backward, and weak sideway scatterings are found in the Ca + HCl → CaCl + H molecular reaction. The results demonstrate that the initial rotational-excited state of j = 3 results in more obvious stereodynamics effects.