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A new approach for preventing zero-point energy (ZPE) violation in quasi-classical trajectory (QCT) simulations is presented and applied to H2CO “roaming” reactions. Zero-point energy may be problematic in roaming reactions because they occur at or near bond dissociation thresholds and these channels may be incorrectly open or closed depending on if, or how, ZPE has been treated. Here we run QCT simulations on a “ZPE-corrected” potential energy surface defined as the sum of the molecular potential energy surface (PES) and the global harmonic ZPE surface. Five different harmonic ZPE estimates are examined with four, on average, giving values within 4 kJ/mol—chemical accuracy—for H2CO. The local harmonic ZPE, at arbitrary molecular configurations, is subsequently defined in terms of “projected” Cartesian coordinates and a global ZPE “surface” is constructed using Shepard interpolation. This, combined with a second-order modified Shepard interpolated PES, V, allows us to construct a proof-of-concept ZPE-corrected PES for H2CO, Veff, at no additional computational cost to the PES itself. Both V and Veff are used to model product state distributions from the H + HCO → H2 + CO abstraction reaction, which are shown to reproduce the literature roaming product state distributions. Our ZPE-corrected PES allows all trajectories to be analysed, whereas, in previous simulations, a significant proportion was discarded because of ZPE violation. We find ZPE has little effect on product rotational distributions, validating previous QCT simulations. Running trajectories on V, however, shifts the product kinetic energy release to higher energy than on Veff and classical simulations of kinetic energy release should therefore be viewed with caution. [ABSTRACT FROM AUTHOR]

Finite temperature quantum and anharmonic effects are studied in H2-Li+-benzene, a model hydrogen storage material, using path integral Monte Carlo (PIMC) simulations on an interpolated potential energy surface refined over the eight intermolecular degrees of freedom based upon M05-2X/6- 311+G(2df,p) density functional theory calculations. Rigid-body PIMC simulations are performed at temperatures ranging from 77 K to 150 K, producing both quantum and classical probability density histograms describing the adsorbed H2. Quantum effects broaden the histograms with respect to their classical analogues and increase the expectation values of the radial and angular polar coordinates describing the location of the center-of-mass of the H2 molecule. The rigid-body PIMC simulations also provide estimates of the change in internal energy, ΔUads, and enthalpy, ΔHads, for H2 adsorption onto Li+-benzene, as a function of temperature. These estimates indicate that quantum effects are important even at room temperature and classical results should be interpreted with caution. Our results also show that anharmonicity is more important in the calculation of U and H than coupling-coupling between the intermolecular degrees of freedom becomes less important as temperature increases whereas anharmonicity becomes more important. The most anharmonic motions in H2-Li+-benzene are the "0helicopter" and "ferris wheel" H2 rotations. Treating these motions as one-dimensional free and hindered rotors, respectively, provides simple corrections to standard harmonic oscillator, rigid rotor thermochemical expressions for internal energy and enthalpy that encapsulate the majority of the anharmonicity. At 150 K, our best rigid-body PIMC estimates for ΔUads and ΔHads are -13.3 ± 0.1 and -14.5 ± 0.1 kJ mol-1, respectively. [ABSTRACT FROM AUTHOR]

Quantum and anharmonic effects are investigated in (H2)2-Li+-benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials, using rigid-body diffusion Monte Carlo (RBDMC) simulations. The potential-energy surface (PES) is calculated as a modified Shepard interpolation of M05-2X/6-311+G(2df,p) electronic structure data. The RBDMC simulations yield zero-point energies (ZPE) and probability density histograms that describe the groundstate nuclear wavefunction. Binding a second H2 molecule to the H2-Li+-benzene complex increases the ZPE of the system by 5.6 kJ mol-1 to 17.6 kJ mol-1. This ZPE is 42% of the total electronic binding energy of (H2)2-Li+-benzene and cannot be neglected. Our best estimate of the 0 K binding enthalpy of the second H2 to H2-Li+-benzene is 7.7 kJ mol-1, compared to 12.4 kJ mol-1 for the first H2 molecule. Anharmonicity is found to be even more important when a second (and subsequent) H2 molecule is adsorbed; use of harmonic ZPEs results in significant error in the 0 K binding enthalpy. Probability density histograms reveal that the two H2 molecules are found at larger distance from the Li+ ion and are more confined in the coordinate than in H2-Li+-benzene. They also show that both H2 molecules are delocalized in the azimuthal coordinate, f. That is, adding a second H2 molecule is insufficient to localize the wavefunction in f. Two fragment-based (H2)2-Li+-benzene PESs are developed. These use a modified Shepard interpolation for the Li+-benzene and H2-Li+-benzene fragments, and either modified Shepard interpolation or a cubic spline to model the H2-H2 interaction. Because of the neglect of three-body H2, H2, Li+ terms, both fragment PESs lead to overbinding of the second H2 molecule by 1.5 kJ mol-1. Probability density histograms, however, indicate that the wavefunctions for the two H2 molecules are effectively identical on the "full" and fragment PESs. This suggests that the 1.5 kJ mol-1 error is systematic over the regions of configuration space explored by our simulations. Notwithstanding this, modified Shepard interpolation of the weak H2-H2 interaction is problematic and we obtain more accurate results, at considerably lower computational cost, using a cubic spline interpolation. Indeed, the ZPE of the fragment-with-spline PES is identical, within error, to the ZPE of the full PES. This fragmentation scheme therefore provides an accurate and inexpensive method to study higher hydrogen loading in this and similar systems. [ABSTRACT FROM AUTHOR]

Carbonyls are among the most abundant volatile organic compounds in the atmosphere. They are central to atmospheric photochemistry as absorption of near-UV radiation by the C=O chromophore can lead to photolysis. If photolysis does not occur on electronic excited states, non-radiative relaxation to the ground state will form carbonyls with extremely high internal energy. These 'hot' molecules can access a range of ground state reactions. Up to nine potential ground state reactions are investigated at the B2GP-PLYP-D3/def2-TZVP level of theory for a dataset of 20 representative carbonyls. Almost all are energetically accessible under tropospheric conditions. Comparison with experiment suggests the most significant ground state dissociation pathways will be concerted triple fragmentation in saturated aldehydes, Norrish type III dissociation to form another carbonyl, and H2--loss involving the formyl H atom in aldehydes. Tautomerisation, leading to more reactive unsaturated species, is also predicted to be energetically accessible and is likely to be important when there is no low-energy ground state dissociation pathway, for example in α,β-unsaturated carbonyls and some ketones. The concerted triple fragmentation and H2--loss pathways have immediate atmospheric implication to global H[sub 2] production and tautomerisaton has implication to the atmospheric production of organic acids. [ABSTRACT FROM AUTHOR]

We outline an approach for building molecular dipole moment surfaces using modified Shepard interpolation. Our approach is highly automated, requires minimal parameterization, and is iteratively improvable. Using the water molecule as a test case, we investigate how different aspects of the interpolation scheme affect the rate of convergence of calculated IR spectral line intensities. It is found that the interpolation scheme is sensitive to coordinate singularities present at linear geometries. Due to the generally monotonic nature of the dipole moment surface, the one-part weight function is found to be more effective than the more complicated two-part variant, with first-order interpolation also giving better-than-expected results. Almost all sensible schemes for choosing interpolation reference data points are found to exhibit acceptable convergence behavior. [ABSTRACT FROM AUTHOR]

Quantum and anharmonic effects are investigated in H2-Li+-benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials. Three- and 8-dimensional quantum diffusion Monte Carlo (QDMC) and rigid-body diffusion Monte Carlo (RBDMC) simulations are performed on potential energy surfaces interpolated from electronic structure calculations at the M05-2X/6-31+G(d,p) and M05-2X/6-311+G(2df,p) levels of theory using a three-dimensional spline or a modified Shepard interpolation. These calculations investigate the intermolecular interactions in this system, with three- and 8-dimensional 0 K H2 binding enthalpy estimates, ΔHbind(0 K), being 16.5 kJ mol-1 and 12.4 kJ mol-1, respectively: 0.1 and 0.6 kJ mol-1 higher than harmonic values. Zero-point energy effects are 35% of the value of ΔHbind (0 K) at M05-2X/6-311+G(2df,p) and cannot be neglected; uncorrected electronic binding energies overestimate ΔHbind (0 K) by at least 6 kJ mol-1. Harmonic intermolecular binding enthalpies can be corrected by treating the H2 "helicopter" and "ferris wheel" rotations as free and hindered rotations, respectively. These simple corrections yield results within 2% of the 8-dimensional anharmonic calculations. Nuclear ground state probability density histograms obtained from the QDMC and RBDMC simulations indicate the H2 molecule is delocalized above the Li+-benzene system at 0 K. [ABSTRACT FROM AUTHOR]

The response of a molecule to an electric field E, often a model of environment, can be expressed in terms of a sum of power series expansions. We investigate the accuracy and limits of applicability of this expression using one-, two-, and three-dimensional models of the hydrogen-bonded complex, ClH:NH3. Energetic, structural, and vibrational spectroscopic characteristics are determined at first- and second-order in E and ∇E and compared with ab initio values for a range of uniform and non-uniform electric fields chosen to simulate molecular environments. It is found that even at field strengths large enough to cause dramatic structural change in the complex, energetic, structural, and vibrational spectroscopic characteristics are accurately calculated using only terms linear in E and ∇E. These results suggest that knowledge of the zero-field molecular potential energy, dipole, and quadrupole moment surfaces may be sufficient to accurately model the interaction of a molecule with a wide range of chemical environments. [ABSTRACT FROM AUTHOR]

One of the largest remaining errors in thermochemical calculations is the determination of the zero-point energy (ZPE). The fully coupled, anharmonic ZPE and ground state nuclear wave function of the SSSH radical are calculated using quantum diffusion Monte Carlo on interpolated potential energy surfaces (PESs) constructed using a variety of method and basis set combinations. The ZPE of SSSH, which is approximately 29 kJ mol-1 at the CCSD(T)/6-31G* level of theory, has a 4 kJ mol-1 dependence on the treatment of electron correlation. The anharmonic ZPEs are consistently 0.3 kJ mol-1 lower in energy than the harmonic ZPEs calculated at the Hartree–Fock and MP2 levels of theory, and 0.7 kJ mol-1 lower in energy at the CCSD(T)/6-31G* level of theory. Ideally, for sub-kJ mol-1 thermochemical accuracy, ZPEs should be calculated using correlated methods with as big a basis set as practicable. The ground state nuclear wave function of SSSH also has significant method and basis set dependence. The analysis of the nuclear wave function indicates that SSSH is localized to a single symmetry equivalent global minimum, despite having sufficient ZPE to be delocalized over both minima. As part of this work, modifications to the interpolated PES construction scheme of Collins and co-workers are presented. [ABSTRACT FROM AUTHOR]

The dynamics of the photodissociation of CH3CHO into CH3+HCO products have been investigated at energies between 30 953 and 31 771 cm-1, spanning the threshold for radical production on the triplet (T1) surface. A barrierless pathway to CH3+HCO radical products formed on the ground state (S0) surface was discovered and established to be an important reaction channel in acetaldehyde photodissociation throughout this wavelength range. HCO laser induced fluorescence (LIF) spectra recorded from CH3CHO dissociated above and below the T1 barrier energy are quite different; HCO produced on S0 yields a more congested LIF spectrum with sharp rotational transitions, while HCO formed on the T1 surface displays fewer, more intense, Doppler-broadened lines. These differences have been further explored in the populations of the HCO Ka=1 doublets. Despite the upper and lower levels being almost isoenergetic, HCO formed on T1 preferentially populates the upper Kc state due to the geometry of the T1 transition state structure. In contrast, HCO formed on S0 produces equal population in each of the upper and lower Ka=1 components. Product state distributions (PSDs) showed that HCO formed on S0 is born with an approximately statistical distribution of population in the available product states, modeled well by phase space theory. HCO formed on the T1 surface, in contrast, has a PSD that can be characterized as arising from “impulsive” dynamics. Previous discrepancies in the height of the T1 barrier are discussed following the observation that, once the T1 channel is energetically accessible, there is competition between the S0 and T1 pathways, with the dominance of the triplet channel increasing with increasing photolysis energy. [ABSTRACT FROM AUTHOR]

Previous experimental and theoretical studies of the radical dissociation channel of T1 acetaldehyde show conflicting behavior in the HCO and CH3 product distributions. To resolve these conflicts, a full-dimensional potential-energy surface for the dissociation of CH3CHO into HCO and CH3 fragments over the barrier on the T1 surface is developed based on RO-CCSD(T)/cc-pVTZ(DZ) ab initio calculations. 20 000 classical trajectories are calculated on this surface at each of five initial excess energies, spanning the excitation energies used in previous experimental studies, and translational, vibrational, and rotational distributions of the radical products are determined. For excess energies near the dissociation threshold, both the HCO and CH3 products are vibrationally cold; there is a small amount of HCO rotational excitation and little CH3 rotational excitation, and the reaction energy is partitioned dominantly (>90% at threshold) into relative translational motion. Close to threshold the HCO and CH3 rotational distributions are symmetrically shaped, resembling a Gaussian function, in agreement with observed experimental HCO rotational distributions. As the excess energy increases the calculated HCO and CH3 rotational distributions are observed to change from a Gaussian shape at threshold to one more resembling a Boltzmann distribution, a behavior also seen by various experimental groups. Thus the distribution of energy in these rotational degrees of freedom is observed to change from nonstatistical to apparently statistical, as excess energy increases. As the energy above threshold increases all the internal and external degrees of freedom are observed to gain population at a similar rate, broadly consistent with equipartitioning of the available energy at the transition state. These observations generally support the practice of separating the reaction dynamics into two reservoirs: an impulsive reservoir, fed by the exit channel dynamics, and a statistical reservoir, supported by the random distribution of excess energy above the barrier. The HCO rotation, however, is favored by approximately a factor of 3 over the statistical prediction. Thus, at sufficiently high excess energies, although the HCO rotational distribution may be considered statistical, the partitioning of energy into HCO rotation is not. [ABSTRACT FROM AUTHOR]

A modified Shepard interpolation scheme is used to construct global potential energy surfaces (PES) in order to calculate quantum observables—vibrationally averaged internal coordinates, fully anharmonic zero-point energies and nuclear radial distribution functions—for a prototypical loosely bound molecular system, the water dimer. The efficiency of PES construction is examined with respect to (a) the method used to sample configurational space, (b) the method used to choose which points to add to the PES data set, and (c) the use of either a one- or two-part weight function. The most efficient method for constructing the PES is found to require a quantum sampling regime, a combination of both h-weight and rms methods for choosing data points and use of the two-part weight function in the interpolation. Using this regime, the quantum diffusion Monte Carlo zero-point energy converges to the exact result within addition of 50 data points. The vibrationally averaged O–O distance and O–O radial distribution function, however, converge more slowly and require addition of over 500 data points. The methods presented here are expected to be applicable to both other loosely bound complexes as well as tightly bound molecular species. When combined with high quality ab initio calculations, these methods should be able to accurately characterize the PES of such species. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The quantum dynamical nature of hydrogen bonding in 1,2-ethanediol and monohydrated 1,2-ethanediol using different levels of ab initio theory is investigated. The degree of proton delocalization and shortening of the vibrationally averaged O-O distance was found to be dependent on the ab initio method used to generate the potential energy surface (PES) data set.

The first experimental observation of the primary photochemical channel of acetaldehyde leading to the formation of ketene (CH2CO) and hydrogen (H2) molecular products is reported. Acetaldehyde (CH3CHO) was photolysed in a molecular beam at 305.6 nm and the resulting H2 product characterized using velocity-map ion (VMI) imaging. Resonance-enhanced multiphoton ionization (REMPI), via two-photon excitation to the double-well EF 1Σ+g state, was used to state-selectively ionize the H2 and determine angular momentum distributions for H2 (ν = 0) and H2 (ν = 1). Velocity-map ion images were obtained for H2 (ν = 0 and 1, J = 5), allowing the total translational energy release of the photodissociation process to be determined. Following photolysis of CH3CHO in a gas cell, the CH2CO co-fragment was identified, using Fourier transform infrared spectroscopy, by its characteristic infrared absorption at 2150 cm−1. The measured quantum yield of the CH2CO + H2 product channel at 305.0 nm is Φ = 0.0075 ± 0.0025 for both 15 Torr of neat CH3CHO and a mixture with 745 Torr of N2. Although small, this result has implications for the atmospheric photochemistry of carbonyls and this reaction represents a new tropospheric source of H2. Quasi-classical trajectory (QCT) simulations on a zero-point energy corrected reaction-path potential are also performed. The experimental REMPI and VMI image distributions are not consistent with the QCT simulations, indicating a non reaction-path mechanism should be considered. [ABSTRACT FROM AUTHOR]

In this paper we demonstrate, at the UHF/6-311++G(d,p) level of theory, the practical feasibility of using ab initio quantum chemical calculations to generate a molecular potential energy surface (PES) for the OH+H2→H2O+H reaction using our previously suggested interpolation and iteration schemes. The successful, and almost completely automated, merger of the PES algorithm and quantum chemical calculations involves a number of significant practical problems, the solutions of which are presented in detail. The convergence of the interpolated potential surface was monitored in terms of reaction probability and we find that the surface converges once the energy, gradient and Hessian have been calculated at approximately 350 geometries. We also find that, although the initial geometries used consisted only of points along a reaction path for the OH+H2→H2O+H reaction, the potential energy surface iteration process rapidly adds information about other, energetically accessible, reaction channels. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this paper we evaluate the use of higher order derivatives in the construction of an interpolated potential energy surface for the OH+H2→H2O+H reaction. The surface construction involves interpolating between local Taylor expansions about a set of known data points. We examine the use of first, second, third, and fourth order Taylor expansions in the interpolation scheme. The convergence of the various interpolated surfaces is evaluated in terms of the probability of reaction. We conclude that first order Taylor expansions (and by implication zeroth order expansions) are not suitable for constructing potential energy surfaces for reactive systems. We also conclude that it is inefficient to use fourth order derivatives. The factors differentiating between second and third order Taylor expansions are less clear. Although third order surfaces require substantially fewer data points to converge than second order surfaces, this faster convergence does not offset the large cost incurred in calculating numerical third derivatives. We therefore conclude that, without an efficient means for calculating analytic third derivatives, second order derivatives provide the most cost-effective means of constructing a global potential energy surface by interpolation. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Trajectory data are reported for the reaction CH4+H→CH3+H2, designed to provide information that can be used to test approximate quantitative theories for the dynamics of abstraction reactions. A potential function was devised which properly reflects the nuclear permutation symmetry of the process. Microscopic reaction rate coefficients were obtained as functions of fixed rotational and vibrational energy, and of the angular momentum. The data indicated significant uncoupling between the various modes although, at a minimum, the symmetric stretch is directly coupled to the reaction coordinate at the transition state. The data were used to test the assumption that the total angular momentum, J, may be approximated by the orbital angular momentum, L. L is approximately conserved from the reactant to the saddle point configuration in reactive and nonreactive collisions and may be well approximated by J. The angular momentum about the long axis of the reacting system (equivalent to the K quantum number) is not conserved in either reactive or nonreactive trajectories. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A recently proposed scheme for interpolating and iteratively improving molecular potential energy surfaces [Ischtwan and Collins, J. Chem. Phys. 100, 8080 (1994)] is evaluated by comparison with an analytic surface for the OH+H2→H2O+H reaction. An improvement in the procedure for constructing the potential surface is suggested and implemented. The most efficient means of converging the surface is determined. It is found that the probability of reaction, for example, may be accurately calculated using of the order of 200–400 data points to define the potential energy surface. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

EOM-CCSD calculations are performed to evaluate two-bond (super 35)Cl-(super 15)N spin-spin coupling constants [(super 2h)J(sub Cl-N)] across the hydrogen bond in ClH:NH3 complexes. The resulting effect of the external electric fields on the nature of the hydrogen bond is analyzed.

A general method is presented for constructing, from ab initio quantum chemistry calculations, the potential energy surface (PES) for H2 absorbed in a porous crystalline material. The method is illustrated for the metal-organic framework material MOF-5. Rigid body quantum diffusion Monte Carlo simulations are used in the construction of the PES and to evaluate the quantum ground state of H2 in MOF-5, the zero-point energy, and the enthalpy of adsorption at 0 K. [ABSTRACT FROM AUTHOR]