Ground-state Reaction Research Articles

Adiabatic Capture Theory Applied to N + NH → N2 + H at Low Temperature

The adiabatic capture centrifugal sudden approximation (ACCSA) has been applied to the ground state reaction N+NH-->N2+H over the temperature range 2-300 K using an existent potential energy surface. The resultant thermal rate constants are in agreement with available rate constants from quasi-classical trajectory calculations but are significantly larger than the available experimentally derived rate. The calculated rate constants monotonically increase with increasing temperature but could only be approximately described with a simple Arrhenius-like form. Subtle quantum effects are evident in the initial rotational state resolved cross sections and rate constants.

State-Resolved Reactivity of CH4(2ν3) on Pt(111) and Ni(111): Effects of Barrier Height and Transition State Location

Quantum state-resolved sticking coefficients on Pt(111) and Ni(111) surfaces have been measured for CH4 excited to the first overtone of the antisymmetric C-H stretch (2nu3) at well-defined kinetic energies in the range of 10-90 kJ/mol. The ground-state reactivity of CH4 is approximately 3 orders of magnitude lower on Ni(111) than on Pt(111) for kinetic energies in the range of 10-64 kJ/mol, reflecting a difference in barrier height of 28+/-6 kJ/mol. 2nu3 excitation of CH4 increases its reactivity by more than 4 orders of magnitude on Ni(111), whereas on Pt(111) the reactivity increase is lower by 2 orders of magnitude. We discuss the observed differences in the state-resolved reactivity for the ground state and 2nu3 excited state of methane in terms of a difference in barrier height and transition state location for the dissociation reaction on the two metal surfaces.

Seven dimensional quantum dynamics study of the H2+NH2→H+NH3 reaction

Initial state-selected time-dependent wave packet dynamics calculations have been performed for the H2+NH2-->H+NH3 reaction using a seven dimensional model on an analytical potential energy surface based on the one developed by Corchado and Espinosa-Garcia [J. Chem. Phys. 106, 4013 (1997)]. The model assumes that the two spectator NH bonds are fixed at their equilibrium values and nonreactive NH2 group keeps C2v symmetry and the rotation-vibration coupling in NH2 is neglected. The total reaction probabilities are calculated when the two reactants are initially at their ground states, when the NH2 bending mode is excited, and when H2 is on its first vibrational excited state, with total angular momentum J=0. The converged cross sections for the reaction are also reported for these initial states. Thermal rate constants and equilibrium constants are calculated for the temperature range of 200-2000 K and compared with transition state theory results and the available experimental data. The study shows that (a) the reaction is dominated by ground-state reactivity and the main contribution to the thermal rate constants is thought to come from this state, (b) the excitation energy of H2 was used to enhance reactivity while the excitation of the NH2 bending mode hampers the reaction, (c) the calculated thermal rate constants are very close to the experimental data and transition state theory results at high and middle temperature, while they are ten times higher than that of transition state theory at low temperature (T=200 K), and (d) the equilibrium constants results indicate that the approximations applied may have different roles in the forward and reverse reactions.

Experimental and Theoretical Studies of the Reactions Y (a2D) + H2CO and Y (a2D) + CH3CHO

The reactions of ground state Y (a(2)D) with H(2)CO and CH(3)CHO were studied at a range of collision energies in crossed molecular beams. For reaction with H(2)CO, three product channels were observed: formation of YH(2) + CO, YCO + H(2), and YHCO + H. Reaction with CH(3)CHO led to three analogous product channels involving formation of HYCH(3) + CO, YCH(2)CO + H(2), and YCH(3)CO + H. The calculated CCSD(T) energetics and DFT geometries for key intermediates in both reactions, together with RRKM theory, are used to calculate a priori the branching ratios between various product channels. These calculated values are compared to those obtained experimentally.

An eight-degree-of-freedom, time-dependent quantum dynamics study for the H2+C2H reaction on a new modified potential energy surface

An eight-dimensional time-dependent quantum dynamics wave packet approach is performed for the study of the H2+C2H-->H+C2H2 reaction system on a new modified potential energy surface (PES) [L.-P. Ju et al., Chem. Phys. Lett. 409, 249 (2005)]. This new potential energy surface is obtained by modifying Wang and Bowman's old PES [J. Chem. Phys. 101, 8646 (1994)] based on the new ab initio calculation. This new modified PES has a much lower transition state barrier height at 2.29 kcal/mol than Wang and Bowman's old PES at 4.3 kcal/mol. This study shows that the reactivity for this diatom-triatom reaction system is enhanced by vibrational excitations of H2, whereas the vibrational excitations of C2H only have a small effect on the reactivity. Furthermore, the bending excitations of C2H, compared to the ground state reaction probability, hinder the reactivity. The comparison of the rate constant between this calculation and experimental results agrees with each other very well. This comparison indicates that the new modified PES corrects the large barrier height problem in Wang and Bowman's old PES.

A Theoretical Characterization of the Photoisomerization Channels of 1,2-Cyclononadienes on both Singlet and Triplet Potential-Energy Surfaces

The ground-, (1)(pipi*)-, and (3)(pipi*)-state potential-energy surfaces of 1,2-cyclononadiene and isomeric C(9)H(14) species, as well as 1-methyl-1,2-cyclononadiene and isomeric C(10)H(16) species were all mapped using CASSCF and the 6-31G(d) basis set. Theoretical results were found to be in good agreement with the available experimental observations for both 1,2-cyclononadiene and 1-methyl-1,2-cyclononadiene isomerization reactions under singlet and triplet direct or sensitized irradiation. Extremely efficient decay occurs from the first singlet excited state to the ground state through at least three different conical intersections (surface crossings). The first of these crossing points is accessed by a one-bond ring closure. From this conical intersection point (CI-A or CI-C), some possible subsequent ground-state reaction paths have been identified: 1) intramolecular C--H bond insertion to form the bicyclic photoproduct and 2) intramolecular C--H bond insertion to form tricyclic photoproducts. An excited state [1,3]-sigmatropic shift leads to the second conical intersection (CI-B or CI-E), which can give a three-bond cyclononyne species. Besides these, in the singlet photochemical reactions of 1-methyl-1,2-cyclononadiene, excited-state, one allenic C--H bond insertion leads to a third conical intersection (CI-D). Possible ground-state reaction pathways from this structure lead to the formation of a diene photoproduct or to transannular insertion photoproducts. Moreover, in the case of triplet 1,2-cyclononadiene and 1-methyl-1,2-cyclononadiene photoisomerization reactions, both chemical reactions will adopt a 1,3-biradical (T(1)/S(0)-1, T(1)/S(0)-2, and T(1)/S(0)-3), which may undergo intersystem crossings leading to the formation of tricyclic or bicyclic photoproducts. The results obtained allow a number of predictions to be made.

Searching for resonances in the reaction Cl+CH4→HCl+CH3: Quantum versus quasiclassical dynamics and comparison with experiments

A quantum-mechanical (QM) and quasiclassical trajectory (QCT) study was performed on the title reaction, using a pseudotriatomic ab initio based surface. Probabilities and integral cross sections present some clear peaks versus the collision energy E(col), which we assign to Feshbach resonances of the transition state, where the light H atom oscillates between the heavy Cl and CH(3) groups. For ground-state reactants, reactivity is essentially of quantum origin (QCT observables and oscillations are smaller, or much smaller, than QM ones), and the calculated integral cross section and product distributions are in reasonable agreement with the experiment. The reaction occurs through an abstraction mechanism, following both a direct and an indirect mechanism. The quasiclassical trajectory calculations show the participation of a short-lived collision complex in the microscopic reaction mechanism. Finally, QCT differential cross sections of Cl+CH(4)-->HCl (nu(')=0 and 1)+CH(3) oscillate versus E(col), whereas experimentally this only occurs for HCl (nu(')=1). This theoretical result and other oscillating properties found here could, however, be related to the existence of a Feshbach resonance for the production of HCl (nu(')=1), as suggested by experimentalists.

Role of the C−H Stretch Mode Excitation in the Dynamics of the Cl + CHD3 Reaction: A Quasi-classical Trajectory Calculation

To analyze the effect of the C-H stretch mode excitation on the dynamics of the Cl + CHD3 gas-phase abstraction reaction, an exhaustive state-to-state dynamics study was performed. This reaction can evolve along two channels: H-abstraction, CD3 + ClH, and D-abstraction, CHD2 + ClD. On an analytical potential energy surface constructed previously by our group, named PES-2005, quasi-classical trajectory calculations were performed at a collision energy of 0.18 eV, including corrections to avoid zero-point energy leakage along the trajectories. First, strong coupling between different vibrational modes in the entry valley was observed; i.e., the reaction is vibrationally nonadiabatic. Second, for the ground-state CHD3(nu=0) reaction, the diatomic fragments appeared in their ground states, and the H- and D-abstraction reactions showed similar reactivities. However, when the reactivity per atom is considered, the H is three times more reactive than the D atom. Third, when the C-H stretch mode is excited by one quantum, CHD3(nu1=1), the H-abstraction is strongly favored, and the C-H stretch excitation is maintained in the product CHD2(nu1=1) + ClD channel; i.e., the reaction shows mode selectivity, reproducing the experimental evidence, and also the reactivity of the vibrational ground state is increased, in agreement with experiment. Fourth, the state-to-state angular distributions of the CD3 and CHD2 products showed the products to be practically sideways for the reactant ground state, while the C-H excitation yielded a more forward scattering, reproducing the experimental data. The role of the zero-point energy correction was also analyzed, and we find that the dynamics results are very sensitive on how the ZPE issue is treated. Finally, a comparison is made with the similar H + CHD3(nu1=0,1) and Cl + CH4(nu1=0,1) reactions.

State-to-state reaction probabilities for the H+O2(v,j)→O+OH(v′,j′) reaction on three potential energy surfaces

We report state-to-state and total reaction probabilities for J=0 and total reaction probabilities for J=2 and 4 for the title reaction, both for ground-state and initially rovibrationally excited reactants. The results for three different potential energy surfaces are compared and contrasted. The potential energy surfaces employed are the DMBE IV surface by Pastrana et al. [J. Phys. Chem. 94, 8073 (1990)], the surface by Troe and Ushakov (TU) [J. Chem. Phys. 115, 3621 (2001)], and the new XXZLG ab initio surface by Xu et al. [J. Chem. Phys. 122, 244305 (2005)]. Our results show that the total reaction probabilities from both the TU and XXZLG surfaces are much smaller in magnitude for collision energies above 1.2 eV compared to the DMBE IV surface. The three surfaces also show different behavior with regards to the effect of initial state excitation. The reactivity is increased on the XXZLG and the TU surfaces and decreased on the DMBE IV surface. Vibrational and rotational product state distributions for the XXZLG and the DMBE IV surface show different behaviors for both types of distributions. Our results show that for energies above 1.25 eV the dynamics on the DMBE IV surface are not statistical. However, there is also evidence that the dynamics on the XXZLG surface are not purely statistical for energies above the onset of the first excited product vibrational state v'=1. The magnitude of the total reaction probability is decreased for J>0 for the DMBE IV and the XXZLG surfaces for ground-state reactants. However, for initially rovibrationally excited reactants, the total reaction probability does not decrease as expected for both surfaces. As a result the total cross section averaged over all Boltzmann accessible rotational states may well be larger than the cross section reported in the literature for j=1.

Pair-correlated Dynamics of Cl+CHD3(v1=1) Reaction: Effects of Probe Laser Frequency

The reaction of C-H stretch-excited CHD3 with Cl atom was studied in a crossed-beam experiment by imaging of the ground vibrational state of CD3 products. The methyl product was interrogated by (2+1) resonance-enhanced multiphoton ionization via the Q-head of the origin band. We found that the observed image appearances depend sensitively on the precise frequency of the probe laser. We attributed the effects to the slight differences in the subset of N-levels of CD3(v=0) being sampled. The implication of collision dynamics is that compared to the ground-state reaction, the CH stretch-excited reaction preferentially yields rotationally warmer CD3(v=0) products. And a negative correlation between the CD3 rotational excitation and the vibrational excitation of the coincidently formed HCl coproducts was demonstrated, which enabled us to uncover a hidden, stereodynamical aspect of the title reaction.

Conformationally Controlled Chemistry: Excited-State Dynamics Dictate Ground-State Reaction

Ion imaging reveals distinct photodissociation dynamics for propanal cations initially prepared in either the cis or gauche conformation, even though these isomers differ only slightly in energy and face a small interconversion barrier. The product kinetic energy distributions for the hydrogen atom elimination channels are bimodal, and the two peaks are readily assigned to propanoyl cation or hydroxyallyl cation coproducts. Ab initio multiple spawning dynamical calculations suggest that distinct ultrafast dynamics in the excited state deposit each conformer in isolated regions of the ground-state potential energy surface, and, from these distinct regions, conformer interconversion does not effectively compete with dissociation.

Model Study on the Pyridine−Dewar Pyridine and Some Related Photoisomerization Reactions

The potential energy surfaces corresponding to the photochemical reactions of pyridine, phosphinine, and arsabenzene have been investigated by employing the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. The thermal (or dark) reactions of these reactant species have also been examined using the same level of theory. The mechanisms of drastic structural change in the excited- and ground-state reactions of pyridine, phosphinine, and arsabenzene and the differences between them are elucidated. The theoretical investigations suggest that conical intersections play a crucial role in their photoisomerization reactions. The results obtained allow a number of predictions to be made.

Chirp-driven vibrational distribution in transition metal carbonyl complexes

In this theoretical study vibrational ladder climbing in transition metal carbonyl complexes, as a possible means to initialize chemical ground state reactions, and the resulting vibrational population distribution using chirped mid-infrared femtosecond laser pulses is investigated. Our model system is MnBr(CO)(5), a strong IR-absorber within an experimentally easily accessible wavelength region. Special emphasis is put on the perturbation due to additional vibrational modes, especially on one, which allows dissociation at low energies. The related potential energy surface for the three representative modes is calculated, whereon quantum dynamics calculations, including the laser-molecule interaction, are performed. No significant coupling could be detected, neither in the bound, nor in the dissociative region. Contrarily, we found a dynamical barrier even for energies high above the dissociation limit. Different vibrational population distributions after the laser excitation of the CO stretching mode could be generated in dependence of the chirp parameters. Based on these findings we simulated the laser excitation corresponding to an experiment by M. Joffre et al., Proc. Natl. Acad. Ssi. U. S. A., 2004, 101(36), 13216-13220, where coherent vibrational ladder climbing in carboxyhemoglobin was demonstrated and we could offer an explanation for an open question, concerning the interpretation of the spectroscopic data.

Dimerization and Double Proton Transfer-Induced Tautomerism of 4(3H)-Pyrimidinone in Solution Studied by IR Spectroscopy and Quantum Chemical Calculations

The tautomerism and dimerization of 4(3H)-pyrimidinone (4(3H)Pyr) in carbon tetrachloride (CCl4) and chloroform (CHCl3) solutions were investigated using IR spectroscopy and quantum chemical calculations. The observed IR spectra in the NH and OH stretching regions clearly revealed the predominance of the keto tautomer in both solvent systems. The enol form only exists in a very small proportion in the CCl4 solution. The tautomeric constant for the two monomers KT[OH/NH] = 0.012 and DeltaE = 2.62 kcal/mol were estimated at 25 degrees C. This result was supported by the self-consistent reaction field/polarizable continuum (SCRF/PCM) calculation at the MP4(full, SDQ)/aug-cc-pVDZ level, which predicted DeltaE = 3.06 kcal/mol in CCl4. In the C=O stretching region, two bands were observed, suggesting the coexistence of two keto structures at equilibrium. The calculated IR spectra indicated that the bands at 1711 and 1675 cm(-1) arise from the keto monomer and keto-keto (KK) ring dimer, respectively. At elevated temperature, the populations of both the keto and enol monomers increased for the CCl4 solution. The present study revealed that the keto <--> enol tautomerization does not occur in the isolated monomer molecule. The double proton transfer (DPT) reaction in the KK ring dimer presumably plays a substantial role in the population increase of the enol monomer. To our knowledge, this may be the first observation of the tautomerization in a model base pair via the temperature-induced ground-state DPT reaction under a nonpolar liquid environment reported so far. This tautomerism can serve as a mimic circumstance for the spontaneous mutations induced by proton transfer in the DNA base pairs.

A comparative mechanistic analysis of the stereoselectivity trends observed in the oxidation of chiral oxazolidinone-functionalized enecarbamates by singlet oxygen, ozone, and triazolinedione

The stereoselectivity in the reactions of the E/ Z enecarbamates 1, equipped with the oxazolidinone chiral auxiliary, has been examined for singlet oxygen ( 1O 2), ozone (O 3), and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in a variety of solvents as a function of temperature. The oxidative cleavage of the alkenyl functionality by 1O 2 and O 3 releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense ( R vs S) of the stereoselectivity in the MDB formation depends on the electronic nature of the oxidant. A high stereoselectivity, substantially dependent on solvent and temperature, is displayed for the reactions with 1O 2, whereas the ground-state reactants O 3 and PTAD are rather unaffected by solvent and temperature variations. The present comparative analysis clearly substantiates our hypothesis of stereoselective vibrational quenching of the attacking 1O 2, whereas O 3 and PTAD are only subject to steric impositions. The electronically excited 1O 2 is sensitive to all three stereochemically relevant structural characteristics embodied in the chiral enecarbamates, namely the R/ S configuration at the C 4 position of the oxazolidinone chiral auxiliary, the Z/ E geometry of the ‘ alkene’ functionality, and R/ S configuration at the C 3′ position of the enecarbamate side chain.

The oxidation pathways of Ti + by acetaldehyde in the gas phase: A density functional theory investigation

Oxidation of Ti + ( 4F and 2F) with acetaldehyde is investigated using density functional theory. Geometries and energies of the reactants, intermediates and products involved in the reaction are located. Our calculations indicate that oxidation occurring on both the quartet and doublet potential energy surfaces starts with encounter complexation followed by three possible pathways: metal-mediated H migration, direct methyl H shift, and/or C–O insertion. The doublet pathways through intersystem crossing from the quartet ground-state reactants are always energetically preferable with respect to the corresponding quartet routes and the most energetically favorable oxidation occurs through C–O insertion on the doublet surface.

Acid−Base Equilibria and Dynamics in Sodium Dodecyl Sulfate Micelles: Geminate Recombination and Effect of Charge Stabilization

The synthetic flavylium salt 4-carboxy-7-hydroxy-4'-methoxyflavylium chloride (CHMF) exhibits two acid-base equilibria in the range of pH 1-8 in both aqueous and micellar sodium dodecyl sulfate (SDS) solutions. The values of pK(a1) and pK(a2) for the cation-zwitterion (AH(2)(+) <--> Z + H(+)) and the zwitterion-base (Z <--> A(-) + H(+)) equilibria increase from 0.73 and 4.84 in water to 2.77 and 5.64 in SDS micelles, respectively. The kinetic study of the Z <--> A(-) + H(+) ground-state reactions in SDS points to the diffusion-controlled protonation of A(-) in the aqueous phase (k(p2w) = 4.2 x 10(10) M(-)(1) s(-)(1)) and in the micelle (k(p2m) = 2.3 x 10(11) M(-)(1) s(-)(1)). The deprotonation rate of Z did not significantly change upon going from water (k(d2) = 6.3 x 10(5) s(-)(1)) to SDS (k(d2) = 5.2 x 10(5) s(-)(1)), in contrast with the behavior of ordinary cationic flavylium salts, for which k(d2) strongly decreases in SDS micelles. These results suggest that deprotonation of the zwitterionic acid is not substantially perturbed by the micellar charge. Electronic excitation of the Z form of CHMF induces fast adiabatic deprotonation of the hydroxyl group of Z() (2.9 x 10(10) s(-)(1) in water and 8.4 x 10(9) s(-)(1) in 0.1 M SDS), followed by geminate recombination on the picosecond time scale. Interestingly, while recombination in water (k(rec) = 1.7 x 10(9) s(-)(1)) occurs preferentially at the carboxylate group, at the SDS micelle surface, recombination (k(rec) = 9.2 x 10(9) s(-)(1)) occurs at the hydroxyl group. The important conclusion is that proton mobility at the SDS micelle surface is substantially reduced with respect to the mobility in water, which implies that geminate recombination should be a general phenomenon in SDS micelles.

A theoretical treatment of the intersystem crossing in the spin–forbidden reaction [formula omitted

The mechanism of the spin–forbidden reaction N ( S 4 ) + CS 2 ( X ∑ g + 1 ) → NS ( X ∏ 2 ) + CS ( X 1 ∑ + ) on both doublet and quartet potential energy surfaces has been investigated at B3LYP, CCSD(T) and CASSCF levels of theory. The minimum energy point (MEX-1) on the doublet–quartet crossing surface is determined using the complete-active-space-self-consistent field (CASSCF) calculations with (3,4), (5,5), (7,6), and (7,7) active spaces with a weighting of 50%/50% to the doublet and quartet states. The minimum energy point (MEX-1) has a Cs structure resembling the intermediate structure 2M-1. The intersystem crossing at the MEX-1 crossing point is taking place, and it is attributed to the stronger spin–orbit coupling (SOC)(50.2–75.5 cm −1) and the barrier (65.01–72.10 kJ/mol) with respect to the ground state reactants N ( S 4 ) + CS 2 ( X ∑ g + 1 ) . This is in close agreement with the experimental observation reporting large rate coefficients.

A full dimensional, nine-degree-of-freedom, time-dependent quantum dynamics study for the H2+C2H reaction

A full dimensional, nine-degree-of-freedom (9DOF), time-dependent quantum dynamics wave packet approach is presented for the study of the H2+C2H-->H+C2H2 reaction system. This is the first full dimensional quantum dynamics study for a diatom-triatom reaction system. The effects of the initial vibrational and rotational excitations of the reactants on the reactivity of this reaction are investigated. This study shows that vibrational excitations of H2 enhance the reactivity; whereas, the vibrational excitations of C2H only have a small effect on the reaction probability. In addition, the bending excitations of C2H, compared to the ground state reaction probability, hinder the reactivity. Comparison of the ground state reaction probabilities of the 9DOF and 8DOF shows the reaction probability from the full dimensional calculation is larger, with more prominent resonance features.

Reduced neutron spectroscopic factors when using potential geometries constrained by Hartree-Fock calculations

We carry out a systematic analysis of angular distribution measurements for selected ground-state to ground-state ($d,p$) and ($p,d$) neutron transfer reactions, including the calcium isotopes. We propose a consistent three-body model reaction methodology in which we constrain the transferred-neutron bound state and nucleon-target optical potential geometries using modern Hartree-Fock calculations. Our deduced neutron spectroscopic factors are found to be suppressed by $~30$% relative to independent-particle shell-model values, from $^{40}\mathrm{Ca}$ through $^{49}\mathrm{Ca}$. The other nuclei studied, ranging from B to Ti, show similar average suppressions with respect to large-basis shell-model expectations. Our results are consistent with deduced spectroscopic strengths for neutrons and protons from intermediate-energy nucleon knockout reactions and for protons from ($e,{e}^{'}p$) reactions on well-bound nuclei.