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PubMed2005

Dissociation of sulfur dioxide by ultraviolet multiphoton absorption between 224 and 232 nm.

Multiphoton excitation and dissociation of SO(2) have been investigated in the wavelength range from 224 to 232 nm. Strong evidence is found for two-photon excitation to the H Rydberg state, followed by dissociation to SO + O and ionization of the SO product by absorption of a third photon. The two-photon excitation is resonantly enhanced via the C (1)B(2) intermediate state, and the two-photon yield spectrum thus bears a strong resemblance to the spectrum of this intermediate. Imaging of the O((3)P(2)), S((1)D(2)), and SO products suggests that, following dissociation of SO(2) from the H state, SO is produced in the A and B electronic states. S((1)D(2)) is produced both from two-photon dissociation of SO(2) to give S((1)D(2)) + O(2) and by single-photon dissociation of SO(+). In the former process, the O(2) is likely formed in all of its lowest three electronic states.

Models, Chemical↗
PubMed2005

Dissociative photoionization and thermochemistry of dihalomethane compounds studied by threshold photoelectron photoion coincidence spectroscopy.

The dissociative photoionization studies have been performed for a set of dihalomethane CH(2)XY (X,Y = Cl, Br, and I) molecules employing the threshold photoelectron photoion coincidence (TPEPICO) technique. Accurate dissociation onsets for the first and second dissociation limits have been recorded in the 10-13 eV energy range, and ionization potentials have been measured for these compounds. By using our experimental dissociation onsets and the known heat of formation of CH(2)Cl(2) molecule, it has been possible to derive the 0 and 298 K heats of formation of all six neutral dihalomethanes as well as their ionic fragments, CH(2)Cl(+), CH(2)Br(+), and CH(2)I(+), to a precision better than 3 kJ/mol. These new measurements serve to fill the lack of reliable experimental thermochemical information on these molecules, correct the old literature values by up to 19 kJ/mol, and reduce their uncertainties. From our thermochemical results it has also been possible to derive a consistent set of bond dissociation energies for the dihalomethanes.

Journal Article↗
PubMed2005

The adsorption and dissociation of O2 on Cu low-index surfaces.

The extended LEPS of O(2)-Cu single crystal plane systems is constructed by means of 5-MP (the 5-parameter Morse potential). Both the adsorption and dissociation of O(2) on Cu low-index surfaces are investigated with extended LEPS in detail. All critical characteristics of the system that we obtain, such as adsorption geometry, binding energy, eigenvalues for vibration, etc., are in good agreement with the experimental results. Our calculated results suggest there are many differences between O(2)-Cu (110) and O(2)-Pd (110) systems. On a Cu (110) surface, O(2) adsorbs in a tilted configuration and there are two lowest energy dissociation channels along the [001] and [10] directions, respectively. We speculate that the adsorption geometry of O(2) on the metal surfaces relates to the lattice constant of metal. Meanwhile, We use the concepts of the molecular dissociation limit and the surface dissociation distance to analyze again the dissociation mechanism of the O(2) on the low-index surfaces.

Journal Article↗
PubMed2005

Collision-induced dissociation of water into ions.

A modification of the central force model (CFM) that describes the dissociation of water molecules into OH- and H+ ions is proposed for molecular dynamics simulations of energetic particle bombardment of water ice. The model keeps all the properties of the CFM but permits charge exchange between oxygen and hydrogen atoms when the water molecule starts to dissociate after collision with an energetic projectile. The reaction products, therefore, have the correct integer charges, -1 and +1 for hydroxyl and a proton. The threshold for the ionic dissociation is corrected to be at the right value, 17.2 eV, in a vacuum. Using the proposed model, total cross-sections for ionic dissociation as functions of the projectile energy are estimated for Ar and C projectiles colliding with water molecules in a vacuum and water ice. Carbon projectiles are demonstrated to produce more dissociated ions at energies lower than 300 eV. Argon projectiles are more effective in breaking the molecules at higher energies.

Journal Article↗
PubMed2005

Dissociative chemisorption and energy transfer for methane on Ir(111).

A 3-parameter local hot spot model of gas-surface reactivity is employed to analyze and predict dissociative sticking coefficients for CH(4) incident on Ir(111) under varied nonequilibrium and equilibrium conditions. One Ir surface oscillator and the molecular vibrations, rotations, and translational energy directed along the surface normal are treated as active degrees of freedom in the 14 dimensional microcanonical kinetics. The threshold energy for CH(4) dissociative chemisorption on Ir(111) derived from modeling molecular beam experiments is E(0) = 39 kJ/mol. Over more than 4 orders of magnitude of variation in sticking, the average relative discrepancy between the beam and theoretically derived sticking coefficients is 88%. The experimentally observed enhancement in dissociative sticking as beam translational energies decrease below approximately 10 kJ/mol is consistent with a parallel dynamical trapping/energy transfer channel that likely fails to completely thermalize the molecules to the surface temperature. This trapping-mediated sticking, indicative of specific energy transfer pathways from the surface under nonequilibrium conditions, should be a minor contributor to the overall dissociative sticking at thermal equilibrium. Surprisingly, the CH(4) dissociative sticking coefficient predicted for Ir(111) surfaces at thermal equilibrium, based on the molecular beam experiments, is roughly 4 orders of magnitude higher than recent measurements on supported nanoscale Ir catalysts at 1 bar pressure, which suggests that substantial improvements in catalyst turnover rates may be possible.

Journal Article↗
PubMed2005

Photoinduced omega-bond dissociation in the higher excited singlet (S2) and lowest triplet (T1) states of a benzophenone derivative in solution.

Photochemical properties of photoinduced omega-bond dissociation in p-benzoylbenzyl phenyl sulfide (BBPS) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BBPS was shown to undergo photoinduced omega-bond cleavage to yield the p-benzoylbenzyl radical (BBR) and phenyl thiyl radical (PTR) at room temperature. The quantum yield (phi(rad)) for the radical formation was found to depend on the excitation wavelength, i.e., on the excitation to the excited singlet states, S2 and S1 of BBPS; phi(rad)(S2) = 0.65 and phi(rad)(S1) = 1.0. Based on the CIDEP data, these radicals were found to be produced via the triplet state independent of excitation wavelength. By using triplet sensitization of xanthone, the efficiency (alpha(rad)) of the C-S bond fission in the lowest triplet state (T1) of BBPS was determined to be unity. The agreement between phi(rad)(S1) and alpha(rad) values indicates that the C-S bond dissociation occurs in the T1 state via the S1 state due to a fast intersystem crossing from the S1 to the T1 state. In contrast, the wavelength dependence of the radical yields was interpreted in terms of the C-S bond cleavage in the S2 state competing with internal conversion from the S2 to the S1 state. The smaller value of phi(rad)(S2) than that of phi(rad)(S1) was proposed to originate from the geminate recombination of singlet radical pairs produced by the bond dissociation via the S2 state. Considering the electronic character of the excited and dissociative states in BBPS showed a schematic energy diagram for the omega-bond dissociation of BBPS.

Benzophenones↗
PubMed2005

Ground and excited state dissociation dynamics of ionized 1,1-difluoroethene.

The kinetic energy release distributions (KERDs) for the fluorine atom loss from the 1,1-difluoroethene cation have been recorded with two spectrometers in two different energy ranges. A first experiment uses dissociative photoionization with the He(I) and Ne(I) resonance lines, providing the ions with a broad internal energy range, up to 7 eV above the dissociation threshold. The second experiment samples the metastable range, and the average ion internal energy is limited to about 0.2 eV above the threshold. In both energy domains, KERDs are found to be bimodal. Each component has been analyzed by the maximum entropy method. The narrow, low kinetic energy components display for both experiments the characteristics of a statistical, simple bond cleavage reaction: constraint equal to the square root of the fragment kinetic energy and ergodicity index higher than 90%. Furthermore, this component is satisfactorily accounted for in the metastable time scale by the orbiting transition state theory. Potential energy surfaces corresponding to the five lowest electronic states of the dissociating 1,1-C2H2F2+ ion have been investigated by ab initio calculations at various levels. The equilibrium geometry of these states, their dissociation energies, and their vibrational wavenumbers have been calculated, and a few conical intersections between these surfaces have been identified. It comes out that the ionic ground state X2B1 is adiabatically correlated with the lowest dissociation asymptote. Its potential energy curve increases in a monotonic way along the reaction coordinate, giving rise to the narrow KERD component. Two states embedded in the third photoelectron band (B2A1 at 15.95 eV and C2B2 at 16.17 eV) also correlate with the lowest asymptote at 14.24 eV. We suggest that their repulsive behavior along the reaction coordinate be responsible for the KERD high kinetic energy contribution.

Drug Stability↗
PubMed2006

State-resolved dynamics of the CH(A2Delta) channels from single and multiple photon dissociation of bromoform in the 10-20 eV energy range.

Single photon dissociation of bromoform using synchrotron radiation has been investigated by Fourier transform visible fluorescence spectroscopy (FTVIS). The photodissociation of bromoform in the 12-18 eV energy range results in several products, among which are the CH(A2Delta) and CH(B2Sigma) radicals. Vibrational and rotational state distributions of the CH(A2Delta) are determined from their fluorescence spectra. From the threshold photon energy above which emission from the CH(A2Delta) radicals is observed, the most likely process leading to CH(A) formation is CHBr3 --> CH + 3Br rather than CHBr3 --> CH + Br + Br2. The rotational Boltzmann temperatures in the CH(A --> X) emission spectra for v' = 0 and v' = 1 range between 1570 and 3650 K, depending on the excitation photon energy. From the high rotational excitation, the results suggest that the mechanism for the loss of three bromine atoms is most likely sequential. A small negative emission anisotropy of the CH(A) radicals [(Ipar - Iper)/(Ipar + 2Iper) = -0.024 +/- 0.005] is constant across the action spectrum; a small net absorption dipole of CHBr3 in the vacuum ultraviolet is parallel to the 3-fold symmetry axis of the CHBr3 molecule. The state distributions of the CH(A2Delta) radicals from multiphoton dissociation of bromoform using the 266 nm output (three photons) of a femtosecond laser (Boltzmann temperatures: T(v'=0)(rot)= 4250 +/- 300 K; T(v'=1)(rot)= 3100 +/- 550 K) are compared to those from the single photon dissociation results (Boltzmann temperatures: T(v'=0)(rot)= 3650 +/- 150 K; T(v'=1)(rot)= 2400 +/- 200 K) at the same total excitation energy under collision free conditions. The analysis of the CH(A) rotational populations shows hotter rotational populations for the femtosecond experiment, also suggesting sequential dissociation of the bromoform in the femtosecond experiment. The duration of the femtosecond laser pulse is approximately 180 fs, setting a limit on the time scales for the multiple dissociations.

Journal Article↗
PubMed2006

First principles study of adsorption and dissociation of CO on W(111).

The adsorption and dissociation of carbon monoxide on the W(111) surface is studied with density functional theory. The CO molecule is found to adsorb in end-on configurations (alpha states) and inclined configurations (beta states). The dissociation of the most strongly bound beta state CO is found to have an activation energy of about 0.8 eV, which is lower than the energy required to desorb CO molecularly from the surface. The diffusion of CO and O on W(111) is predicted to be facile at room temperature, whereas C atoms are virtually immobile up to approximately 600 K, according to our calculations. Preadsorbed carbon atoms are shown to prevent the dissociation of CO by blocking the most strongly bound beta state adsorption site and by blocking the dissociation pathway. We predict that dissociation of CO on W(111) is a self-poisoning process.

Journal Article↗
PubMed2006

Effusive molecular beam study of C2H6 dissociation on Pt(111).

The dissociative sticking coefficient for C2H6 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. A microcanonical unimolecular rate theory (MURT) model of the reactive system is used to extract transition state properties from the data as well as to compare our data directly with supersonic molecular beam and thermal equilibrium sticking measurements. We report for the first time the threshold energy for dissociation, E0 = 26.5 +/- 3 kJ mol(-1). This value is only weakly dependent on the other two parameters of the model. A strong surface temperature dependence in the initial sticking coefficient is observed; however, the relatively weak dependence on gas temperature indicates some combination of the following (i) not all molecular excitations are contributing equally to the enhancement of sticking, (ii) that strong entropic effects in the dissociative transition state are leading to unusually high vibrational frequencies in the transition state, and (iii) energy transfer from gas-phase rovibrational modes to the surface is surprisingly efficient. In other words, it appears that vibrational mode-specific behavior and/or molecular rotations may play stronger roles in the dissociative adsorption of C2H6 than they do for CH4. The MURT with an optimized parameter set provides for a predictive understanding of the kinetics of this C-H bond activation reaction, that is, it allows us to predict the dissociative sticking coefficient of C2H6 on Pt(111) for any combination of Ts and Tg even if the two are not equal to one another.

Journal Article↗
PubMed2006

Bromine-loss and hydrogen-loss dissociations in low-lying electronic states of the CH3Br+ ion studied using multiconfiguration second-order perturbation theory.

Complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) calculations with an ANO-RCC basis were performed for the 1(2)A', 1(2)A", 2(2)A', and 2(2)A" states of the CH3Br+ ion. The 1(2)A' state is predicted to be the ground state. The 2(2)A' state is predicted to be a bound state. The adiabatic and vertical excitation energies and the relative energies at the molecular geometry were calculated, and the energetic results for 2(2)A' and 2(2)A" are in reasonable agreement with the experimental data. Potential energy curves (PECs) for Br-loss and H-loss dissociations from the four C(s) states were calculated at the CASPT2//CASSCF level and the electronic states of the CH3(+) and CH2Br(+) ions as the dissociation products were determined by checking the relative energies and geometries of the asymptote products along the PECs. In the Br-loss dissociation, the 1(2)A', 1(2)A", and 2(2)A' states correlate with CH3(+) (X1A1') and the 2(2)A" state correlates with CH3(+) (1(3)A"). The energy increases monotonically with the R(C-Br) value along the four Br-loss PECs. In the H-loss dissociation the 1(2)A', 1(2)A", 2(2)A', and 2(2)A" states correlate with the X(1)A(1), 1(3)A", 1(3)A', and 1(1)A" states (1(3)A' lying above 1(1)A") of CH2Br(+), respectively. Along the 2(2)A" H-loss PEC there is an energy barrier and the CASSCF wave functions at large R(C-H) values have shake-up ionization character. Along the 2(2)A' H-loss PEC there are an energy barrier and a minimum. At the end of the present paper we present a comprehensive review on the electronic states and the X-loss and H-loss dissociations of the CH(3)X(+) (X = F, Cl, and Br) ions on the basis of our previous studies and the present study.

Journal Article↗
PubMed2002

Study of the spontaneous dissociation of rabbit C-reactive protein.

C-Reactive protein (CRP) is composed of five identical noncovalently linked monomers and characterized as an important acute-phase protein. The CRP subunit obtained by denaturing treatments, which is termed modified CRP, has also been widely studied. In the current work, we found that there exists some degree of natural dissociation of CRP in stock solution. This dissociation is critically dependent on the absence of Ca2+. Low pH could enhance the dissociation of CRP, while ionic strength has little effect. Anilinonaphthalenesulfonate (ANS) fluorescence detections indicate that the exposure of hydrophobic surface increases during the dissociation. Acidic pH conditions also induce an increase in ANS fluorescence. This suggests that hydrophobic interactions between CRP subunits may contribute to the study of its pentameric structure. Surface plasmon resonance experiments indicate that monomeric CRP does not specifically bind to phosphatidylcholine-containing membrane as native CRP does. Electron microscopy shows that monomeric CRP binds to negatively charged lipid through electrostatic forces, and such lipid may induce the dissociation of CRP due to the acidic pH in the diffuse double layer near the membrane.

Anilino Naphthalenesulfonates↗
PubMed2002

Acculturation and peritraumatic dissociation in young adult Latino survivors of community violence.

This study examined the relationship between acculturation and peritraumatic dissociation in a sample of 304 physically injured Latino survivors of community violence. Item response theory analyses were conducted to document the measurement equivalence of English- and Spanish-language versions of a scale measuring peritraumatic dissociation. After establishing equivalence, structural equation modeling was used to determine the impact of acculturation on peritraumatic dissociation after controlling for other relevant covariates, including assault characteristics, intoxication before the assault, and trauma exposure history. Acculturation emerged as a significant and negative predictor of dissociation, so that high levels of acculturation were associated with low levels of peritraumatic dissociation. These findings offer a counterinstance to the emerging consensus that retention of Latin American cultural traditions serves to promote mental health.

Acculturation↗
PubMed1998

Invariance in automatic influences of memory: toward a user's guide for the process-dissociation procedure.

Three experiments investigated assumptions of the process-dissociation procedure for separating consciously controlled and automatic influences of memory. Conditions that encouraged direct retrieval revealed process dissociations. Manipulating attention during study or manipulating study time affected recollection but left automatic influences of memory relatively invariant. However, paradoxical dissociations were found when conditions encouraged use of a generate-recognize strategy, violating assumptions underlying the estimation procedure. Use of subjective reports to gain estimates produced parallel results. Easily observed correlations are shown to be not useful for testing assumptions underlying the process-dissociation procedure. A multinomial model produced results that agree with those from the process-dissociation approach.

Automatism↗
PubMed1993

ATP-induced protein-Hsp70 complex dissociation requires K+ but not ATP hydrolysis.

The molecular chaperone proteins, particularly Hsp60 and Hsp70, have been implicated in essential cell functions under both normal and stress conditions (reviewed in refs 1-5). Members of the family of heat-shock proteins of M(r) 70K, Hsp70, bind to unfolded proteins and short peptides. Addition of Mg-ATP results in the dissociation of the substrate polypeptides from the chaperone, but as ATP-gamma S (an ATP analogue that is only slowly hydrolysable) cannot substitute for ATP in this reaction, it has been concluded that ATP hydrolysis is necessary to dissociate Hsp70-substrate protein complexes. By independently measuring the rates of ATP hydrolysis and substrate protein dissociation, we show here that Mg-ATP binding but not Mg-ATP hydrolysis is essential for substrate dissociation. We also show that there is an absolute requirement for K+ for the effect of Mg-ATP: only the combination of K+ and Mg-ATP will cause the conformational change in Hsp70 that is necessary for substrate dissociation. Moreover, in the absence of K+, Mg-ATP favours complex formation. We consider these results in terms of a G-protein-like model.

Adenosine Triphosphatases↗
PubMed2003

Dissociative hydrogen adsorption on palladium requires aggregates of three or more vacancies.

During reaction, a catalyst surface usually interacts with a constantly fluctuating mix of reactants, products, 'spectators' that do not participate in the reaction, and species that either promote or inhibit the activity of the catalyst. How molecules adsorb and dissociate under such dynamic conditions is often poorly understood. For example, the dissociative adsorption of the diatomic molecule H2--a central step in many industrially important catalytic processes--is generally assumed to require at least two adjacent and empty atomic adsorption sites (or vacancies). The creation of active sites for H2 dissociation will thus involve the formation of individual vacancies and their subsequent diffusion and aggregation, with the coupling between these events determining the activity of the catalyst surface. But even though active sites are the central component of most reaction models, the processes controlling their formation, and hence the activity of a catalyst surface, have never been captured experimentally. Here we report scanning tunnelling microscopy observations of the transient formation of active sites for the dissociative adsorption of H2 molecules on a palladium (111) surface. We find, contrary to conventional thinking, that two-vacancy sites seem inactive, and that aggregates of three or more hydrogen vacancies are required for efficient H2 dissociation.

Journal Article↗
PubMed2006

HLA-DM targets the hydrogen bond between the histidine at position beta81 and peptide to dissociate HLA-DR-peptide complexes.

The peptide editor HLA-DM (DM) mediates exchange of peptides bound to major histocompatibility (MHC) class II molecules during antigen processing; however, the mechanism by which DM displaces peptides remains unclear. Here we generated a soluble mutant HLA-DR1 with a histidine-to-asparagine substitution at position 81 of the beta-chain (DR1betaH81N) to perturb an important hydrogen bond between MHC class II and peptide. Peptide-DR1betaH81N complexes dissociated at rates similar to the dissociation rates of DM-induced peptide-wild-type DR1, and DM did not enhance the dissociation of peptide-DR1betaH81N complexes. Reintroduction of an appropriate hydrogen bond (DR1betaH81N betaV85H) restored DM-mediated peptide dissociation. Thus, DR1betaH81N might represent a 'post-DM effect' conformation. We suggest that DM may mediate peptide dissociation by a 'hit-and-run' mechanism that results in conformational changes in MHC class II molecules and disruption of hydrogen bonds between betaHis81 and bound peptide.

Antigen Presentation↗
PubMed2002

Early mechanistic events in biotin dissociation from streptavidin.

The streptavidin-biotin system has provided a unique opportunity to investigate the molecular details of ligand dissociation pathways. An underlying mechanistic question is whether ligand dissociation proceeds with a relatively ordered process of bond breaking and ligand escape. Here we report a joint computational and crystallographic study of the earliest events in biotin dissociation. In molecular dynamics potential of mean force simulations, a water molecule from a defined access channel intercalated into the hydrogen bond between Asp 128 and biotin, bridging them and stabilizing an intermediate state. In forced biotin dissociation simulations, this event led to subsequent bond breaking steps and ligand escape. In equilibrium simulations, the water molecule was sometimes observed to move back to the access channel with re-formation of the biotin hydrogen bond. Analysis of streptavidin crystal structures revealed a close overlap of crystallographically defined and simulated waters in the water access channel. These results suggest that biotin dissociation is initiated by stochastic coupling of water entry with lengthening of a specific biotin hydrogen-bonding interaction.

Aspartic Acid↗