Publications (33)91.85 Total impact
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ABSTRACT: Molecular modelling has become a useful and widely applied tool to investigate separation and diffusion behavior of gas molecules through nanoporous low dimensional carbon materials, including quasi1D carbon nanotubes and 2D graphenelike carbon allotropes. These simulations provide detailed, molecular level information about the carbon framework structure as well as dynamics and mechanistic insights, i.e. size sieving, quantum sieving, and chemical affinity sieving. In this perspective, we revisit recent advances in this field and summarize separation mechanisms for multicomponent systems from kinetic and equilibrium molecular simulations, elucidating also anomalous diffusion effects induced by the confining pore structure and outlining perspectives for future directions in this field.Physical Chemistry Chemical Physics 01/2013; · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: The dynamics of the C((3)P)+OH(X(2)Π) → CO(a(3)Π)+H((2)S) on its second excited potential energy surface, 1(4)A", have been investigated in detail by means of an accurate quantum mechanical (QM) timedependent wave packet (TDWP) approach. Reaction probabilities for values of the total angular momentum J up to 50 are calculated and integral cross sections for a collision energy range which extends up to 0.1 eV are shown. The comparison with quasiclassical trajectory (QCT) and statistical methods reveals the important role played by the double well structure existing in the potential energy surface. The TDWP differential cross sections exhibit a forwardbackward symmetry which could be interpreted as indicative of a complexforming mechanism governing the dynamics of the process. The QM statistical method employed in this study, however, is not capable to reproduce the main features of the possible insertion nature in the reactive collision. The ability to stop individual trajectories selectively at specific locations inside the potential energy surface makes the QCT version of the statistical approach a better option to understand the overall dynamics of the process.The Journal of Chemical Physics 04/2012; 136(16):164309. · 3.12 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: We propose a new route to hydrogen isotope separation which exploits the quantum sieving effect in the context of transmission through asymmetrically decorated, doped porous graphenes. Selectivities of D2 over H2 as well as rate constants are calculated based on ab initio interaction potentials for passage through pure and nitrogen functionalized porous graphene. Onesided dressing of the membrane with metal provides the critical asymmetry needed for an energetically favorable pathway.The Journal of Physical Chemistry C. 03/2012; 116(11). 
Article: Dynamics of the D+ + H2 and H+ + D2 reactions: a detailed comparison between theory and experiment.
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ABSTRACT: An extensive set of experimental measurements on the dynamics of the H(+) + D(2) and D(+) + H(2) ionmolecule reactions is compared with the results of quantum mechanical (QM), quasiclassical trajectory (QCT), and statistical quasiclassical trajectory (SQCT) calculations. The dynamical observables considered include specific rate coefficients as a function of the translational energy, E(T), thermal rate coefficients in the 100500 K temperature range. In addition, kinetic energy spectra (KES) of the D(+) ions reactively scattered in H(+) + D(2) collisions are also presented for translational energies between 0.4 eV and 2.0 eV. For the two reactions, the best global agreement between experiment and theory over the whole energy range corresponds to the QCT calculations using a gaussian binning (GB) procedure, which gives more weight to trajectories whose product vibrational action is closer to the actual integer QM values. The QM calculations also perform well, although somewhat worse over the more limited range of translational energies where they are available (E(T) < 0.6 eV and E(T) < 0.2 eV for the H(+) + D(2) and D(+) + H(2) reactions, respectively). The worst agreement is obtained with the SQCT method, which is only adequate for low translational energies. The comparison between theory and experiment also suggests that the most reliable rate coefficient measurements are those obtained with the merged beams technique. It is worth noting that none of the theoretical approaches can account satisfactorily for the experimental specific rate coefficients of H(+) + D(2) for E(T)≤ 0.2 eV although there is a considerable scatter in the existing measurements. On the whole, the best agreement with the experimental laboratory KES is obtained with the simulations carried out using the state resolved differential cross sections (DCSs) calculated with the QCTGB method, which seems to account for most of the observed features. In contrast, the simulations with the SQCT data predict kinetic energy spectra (KES) considerably cooler than those experimentally determined.Physical Chemistry Chemical Physics 02/2012; 14(10):334659. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: We theoretically extend the applications of graphdiyne, an experimentally available oneatomthin carbon allotrope, to nanoelectronics and superior separation membrane for hydrogen purification on a precise level.Chemical Communications 09/2011; 47(43):118435. · 6.38 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: We present exact quantum integral and differential cross sections for the title reaction from a timedependent wavepacket method which takes account of all Coriolis couplings. We employ two new potential energy surfaces fitted using the double manybody expansion (DMBE) method. The difference between the two surfaces is that for the first the data was extrapolated to the complete basis set limit (CBS) and for the second the data was corrected semiempirically (SEC). While the DMBE/CBS surface is, on first impressions, regarded as the most accurate, our results show that this surface gives consistent smaller cross section when compared to previous results employing an earlier surface, named Ho after its first author. We also find that the DMBE/CBS surface features an unphysical barrier for contracted H(2) distances which explains the smaller results. The DMBE/SEC surface, which is based on the same data, does not show the same barrier and the results compare much better to previous theoretical results as well as those from experiment. While we find that overall the differential cross sections from the DMBE/SEC surface are forward scattered, which is in line with experiment, the cross sections do not rise steeply enough with decreasing energy showing that this surface is not sufficiently attractive at low energies. We find this is due to a shallow van der Waals well present for the Ho surface but not on the DMBE surfaces.Physical Chemistry Chemical Physics 08/2011; 13(30):1364555. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: Rigorous quantum nonadiabatic calculations are carried out on the two coupled electronic states (1(2)A' and 2(2)A') for the C + CH reaction. For all calculations, the initial wave packet was started from the entrance channel of the 1(2)A' state and the initial state of the CH reactant was kept in its ground rovibrational state. Reaction probabilities for total angular momenta J from 0 to 160 are calculated to obtain the integral cross section over an energy range from 0.005 to 0.8 eV collision energy. Significant nonadiabatic effects are found in the reaction dynamics. The branching ratio of the ground state and excited state of C(2) produced is around 0.6, varying slightly with the collision energy. Also, a value of 2.52 × 10(11) cm(3) molecule(1) s(1) for the state selected rate constant k (v = 0, j = 0) at 300 K is obtained, which may be seen as a reference in the future chemical models of interstellar clouds.The Journal of Chemical Physics 07/2011; 135(2):024306. · 3.12 Impact Factor 
Article: Quantum calculations for the S(1D)+H2 reaction employing the ground adiabatic electronic state
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ABSTRACT: We present exact quantum differential and total cross sections for the title reaction. We employ a timedependent wavepacket method as implemented in the DIFFREALWAVE code including all Coriolis coupling and a new potential energy surface, the double manybody expansion/complete basis set (DMBE/CBS) surface. Our results show that the DMBE/CBS surface gives smaller cross section when compared to previous results employing the Ho surface.Physica Scripta 07/2011; 84(2):028102. · 1.03 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: The dynamics of the reaction O((1)D) + HCl → ClO + H, OH + Cl has been investigated in detail by means of a timedependent wave packet (TDWP) method in comparison with quasiclassical trajectory (QCT) and statistical approaches on the ground potential energy surface by Martínez et al. [Phys. Chem. Chem. Phys., 2000, 2, 589]. Fully coupled quantum mechanical (QM) reaction probabilities for high values of the total angular momentum (J≤ 50) are reported for the first time. At the low collision energy regime (E(c)≤ 0.4 eV) the TDWP probabilities are well reproduced by the QCT and statistical results for the ClO forming product channel, but for the OH + Cl arrangement, only QCT probabilities are found to agree with the QM values. The good accordance found between the rigorous statistical models and the dynamical QM and QCT calculations for the O + HCl → ClO + H process underpins the assumption that the reaction pathway leading to ClO is predominantly governed by a complexforming mechanism. In addition, to further test the statistical character of this reaction channel, the laboratory angular distribution and timeofflight spectra obtained in a crossed molecular beam study by Balucani et al. [Chem. Phys. Lett. 1991, 180, 34] at a collision energy as high as 0.53 eV have been simulated using the state resolved differential cross section obtained with the statistical approaches yielding a satisfactory agreement with the experimental results. For the other channel, O + HCl → OH + Cl, noticeable differences between the statistical results and those found with the QCT calculation suggest that the dynamics of the reaction are controlled by a direct mechanism. The comparison between the QCT and QMTDWP results in the whole range of collision energies lends credence to the QCT description of the dynamics of this reaction.Physical Chemistry Chemical Physics 03/2011; 13(18):850214. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A LennardJones atomatom interaction potential is utilized for the description of the interactions between H(2)/D(2) and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouth are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D(2) transport is dramatically favored over H(2). However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficientsimplying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotubeshaped models, throwing into question the common assumption that passage through the pore mouths should be the ratedetermining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantummediated kinetic molecular sieving of H(2)/D(2) in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to poremouth size in order to ensure that the selective step, namely passage through the pore mouth, is also the rate determining step.Physical Chemistry Chemical Physics 03/2011; 13(17):783444. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: We present exact and estimated quantum differential and integral cross sections as well as product state distributions for the title reaction. We employ a timedependent wavepacket method including all Coriolis couplings and also an adapted code where the helicity quantum number and with this the Coriolis couplings have been truncated. Results from helicity truncated as well as helicity conserving (HC) calculation are presented. The HC calculations fail to reproduce the exact results due to the influence of the centrifugal barrier. While the truncated calculation overestimate the exact integral cross sections they reproduce the features of the integral cross section very well. We also find that the product rotational state distributions are well reproduced if the maximum helicity state is chosen carefully. The helicity truncated calculations fail to give a good approximation of differential cross sections.Physical Chemistry Chemical Physics 03/2011; 13(17):794860. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: We present reaction probabilities, branching ratios and vibrational product quantum state distributions for the reaction O(D1)+HCl > OH+Cl (OCl+H), Boltzmann averaged over initial rotational quantum states at a temperature of 300 K and also for the deuterium isotopic variant. The quantum scattering dynamics are performed using the potential energy surfaces for all three contributing electronic states. Comparisons are presented with results computed using only the ground electronic state potential energy surface, with results computed using only the j = 0 initial rotational state and also with results obtained using an equal weighting for the lowest 10 rotational states. Inclusion of the higher initial rotational states significantly changes the form of the reaction probability as a function of collision energy, reducing the threshold for reaction on the 1A '' and 2A' excited electronic states. We found that the combined inclusion of higher initial rotational states and all three contributing electronic states is crucial for obtaining a branching ratio that is within the range and trend given by experiment from our J = 0 calculations. Isotopic effects range from tunnelling effects for the hydrogen variant and enhancement of reactivity for the production of OD on the excited electronic states.01/2011;  [Show abstract] [Hide abstract]
ABSTRACT: We present exact quantum differential cross sections and exact and estimated integral cross sections and branching ratios for the title reaction. We employ a timedependent wavepacket method as implemented in the DIFFREALWAVE code including all Coriolis couplings and also an adapted DIFFREALWAVE code where the helicity quantum number and with this the Coriolis couplings have been truncated. Our exact differential cross sections at 0.453 eV total energy, one of the experimental energies, show good agreement with the experimental results for one of the product channels. While the truncated calculation present a significant reduction in the computational effort needed they overestimate the exact integral cross sections.Physical Chemistry Chemical Physics 10/2010; 12(39):127118. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: Nonadiabatic quantum dynamics calculations on the two coupled potential energy surfaces (PESs) (1(2)A' and 2(2)A') and also adiabatic quantum calculations on the lowest adiabatic PES are reported for the title reaction. Reaction probabilities for total angular momenta, J, varying from 0 to 160, are calculated to obtain the integral cross section (ICS) for collision energies ranging from 0.05 to 1.0 eV. Calculations using both the close coupling and the Centrifugal Sudden (CS) approximation are carried out to evaluate the role of Coriolis coupling effects for this reaction. The results of the nonadiabatic calculations show that the nonadiabatic effects in the title reaction for the initial state of NH (v = 0, j = 0) could be neglected, at least in the collision energy range considered in this study.Physical Chemistry Chemical Physics 09/2010; 12(33):961923. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: A detailed study of the proton exchange reaction H(+) + D(2)(v = 0, j = 0) > HD + D(+) on its ground 1(1)A' potential energy surface has been carried out using 'exact' closecoupled quantum mechanical wavepacket (WPEQM), quasiclassical trajectory (QCT), and statistical quasiclassical trajectory (SQCT) calculations for a range of collision energies starting from the reaction threshold to 1.3 eV. The WPEQM calculations include all total angular momenta up to J(max) = 50, and therefore the various dynamical observables are converged up to 0.6 eV. It has been found that it is necessary to include all Coriolis couplings to obtain reliable converged results. Reaction probabilities obtained using the different methods are thoroughly compared as a function of the total energy for a series of J values. Comparisons are also made of total reaction cross sections as function of the collision energy, and rate constants. In addition, opacity functions, integral cross sections (ICS) and differential cross sections (DCS) are presented at 102 meV, 201.3 meV and 524.6 meV collision energy. The agreement between the three sets of results is only qualitative. The QCT calculations fail to describe the overall reactivity and most of the dynamical observables correctly. At low collision energies, the QCT method is plagued by the lack of conservation of zero point energy, whilst at higher collision energies and/or total angular momenta, the appearance of an effective repulsive potential associated with the centrifugal motion "over" the well causes a substantial decrease of the reactivity. In turn, the statistical models overestimate the reactivity over the whole range of collision energies as compared with the WPEQM method. Specifically, at sufficiently high collision energies the reaction cannot be deemed to be statistical and important dynamical effects seem to be present. In general the WPEQM results lie in between those obtained using the QCT and SQCT methods. One of the main, unexpected, conclusions of this work is that an accurate description of the reaction and of its various dynamical features requires a computationally expensive, accurate quantum mechanical treatment.Physical Chemistry Chemical Physics 02/2010; 12(5):110215. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: We present converged quantum mechanical calculations for the title reaction employing a timedependent wavepacket method. We obtained integral and differential cross sections over an energy range from 0.23 to 0.35 eV total energy as well as product state distributions for both product channels. The excitation functions decrease with energy and point to statistical dynamics as do the cold vibrational distributions and highly inverted rotational distributions. The differential cross sections oscillate strongly with energy for both product channels. Our differential cross sections for both product channels at 2.5 kcal/mol, one of the experimental energies, compare well to the experimental results. The quantum results obtained in this study are similar to what has been found employing QCT methods, implying that the differences between the experimental and theoretical results are due to the potential energy surface or nonadiabatic effects rather than due to quantum effects or the methods employed.Physical Chemistry Chemical Physics 12/2009; 11(48):1158795. · 4.20 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: Real wave packet propagations were carried out on both a single ground electronic state and twocoupledelectronic states of the title reaction to investigate the extent of nonadiabatic effects on the distinguishableatom reaction cross sections. The latest diabatic potential matrix of Abrol and Kuppermann [J. Chem. Phys. 116, 1035 (2002)] was employed in the present nonadiabatic quantum statetostate scattering calculations over a total energy rangefrom threshold (the zero point of the reagent H(2)) to 3.0 eV. Based on the assumption that the hydrogen atoms are distinguishable in the collisions where the inelastic and elastic ones are excluded, no significant nonadiabatic effects have been found in the calculations of the full statetostate integral and differential cross sections up to a total energy of 3.0 eV for product vibrational levels v(')=0, 1, 2, 3. Our results therefore confirm the recent and the previous studies of the geometric phase effects in H+H(2) employing a different diabatic double manybody expansion potential matrix or a different BKMP2 potential energy surface.The Journal of Chemical Physics 05/2009; 130(14):144301. · 3.12 Impact Factor 
Article: Quantum mechanical calculations of the S(1D)+HD reaction dynamics on the ground electronic state
Journal of Physics Conference Series 01/2009;  [Show abstract] [Hide abstract]
ABSTRACT: We present reaction probabilities, branching ratios and vibrational product quantum state distributions for the reaction O(1D)+HCl → OH+Cl (OCl+H), Boltzmann averaged over initial rotational quantum states at a temperature of 300 K and also for the deuterium isotopic variant. The quantum scattering dynamics are performed using the potential energy surfaces for all three contributing electronic states. Comparisons are presented with results computed using only the ground electronic state potential energy surface, with results computed using only the j = 0 initial rotational state and also with results obtained using an equal weighting for the lowest 10 rotational states. Inclusion of the higher initial rotational states significantly changes the form of the reaction probability as a function of collision energy, reducing the threshold for reaction on the 1A" and 2A' excited electronic states. We found that the combined inclusion of higher initial rotational states and all three contributing electronic states is crucial for obtaining a branching ratio that is within the range and trend given by experiment from our J = 0 calculations. Isotopic effects range from tunnelling effects for the hydrogen variant and enhancement of reactivity for the production of OD on the excited electronic states.Journal of Theoretical and Computational Chemistry 01/2009; 08. · 0.52 Impact Factor  [Show abstract] [Hide abstract]
ABSTRACT: A parallel computer code for the calculation of quantum statetostate atom diatom differential reactive cross sections is presented and discussed. The code is based on the real wavepacket approach. The theory underlying the code is discussed and the parallelisation methods used are described. All the input parameters needed by the program are described. Results of test calculations to investigate the scaling properties of the code with grid size and number of processors are presented.Computer Physics Communications 10/2008; 179:569578. · 2.41 Impact Factor
Publication Stats
223  Citations  
91.85  Total Impact Points  
Top Journals
Institutions

2006–2013

University of Queensland
 Australian Institute for Bioengineering and Nanotechnology
Brisbane, Queensland, Australia


2010

Universidad de Salamanca
 Departamento de Química Física
Salamanca, Castile and Leon, Spain


2007–2008

Northeast Institute of Geography and Agroecology
 State Key Laboratory of Molecular Reaction Dynamics
Beijing, Beijing Shi, China


2005

The University of Manchester
 School of Chemistry
Manchester, England, United Kingdom


2000–2003

University of Bristol
 School of Chemistry
Bristol, England, United Kingdom
