Accurate ab initio potential energy surfaces for the (3)A '' and (3)A ' electronic states of the O(P-3) plus HBr system

In this work, we report the construction of potential energy surfaces for the (3)A '' and (3)A' states of the system O(P-3) + HBr. These surfaces are based on extensive ab initio calculations employing the MRCI+Q/CBS+SO level of theory. The complete basis set energies were estimated from extrapolation of MRCI+Q/aug-cc-VnZ(-PP) (n = Q, 5) results and corrections due to spin-orbit effects obtained at the CASSCF/aug-cc-pVTZ(-PP) level of theory. These energies, calculated over a region of the configuration space relevant to the study of the reaction O(P-3) + HBr -> OH + Br, were used to generate functions based on the many-body expansion. The three-body potentials were interpolated using the reproducing kernel Hilbert space method. The resulting surface for the (3)A '' electronic state contains van der Waals minima on the entrance and exit channels and a transition state 6.55 kcal/mol higher than the reactants. This barrier height was then scaled to reproduce the value of 5.01 kcal/mol, which was estimated from coupled cluster benchmark calculations performed to include high-order and core-valence correlation, as well as scalar relativistic effects. The (3)A' surface was also scaled, based on the fact that in the collinear saddle point geometry these two electronic states are degenerate. The vibrationally adiabatic barrier heights are 3.44 kcal/mol for the (3)A '' and 4.16 kcal/mol for the (3)A' state. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4705428]

AM1 and PM3 Calculations of the Potential Energy Surfaces for CH2OH Reactions with NO and NO2

The AM1 and PM3 molecular orbital methods have been utilized to investigate the reactions of CH20H with NO and NO2 PM3 and AM1 calculated heats of formation differ from experimental values by 8.6 and 18.8 kcal mol-', respectively. The dominant reaction of CH20H with NO is predicted to produce the adduct HOCH2N0, supporting the hypothesis of Pagsberg, Munk, Anastasi, and Simpson. Calculated activation energies for the NO2 system predict the formation of the adducts HOCH2N02 and HOCH20N0. In addition, the PM3 calculations predict that the abstraction reaction producing CH20 and HN02 is more likely than one producing CH20 and HONO from reactions of CH20H with NO2.

Exploration of the Potential Energy Surfaces, Prediction of Atmospheric Concentrations, and Prediction of Vibrational Spectra for the HO2···(H2O)n (n = 1−2) Hydrogen Bonded Complexes

The hydroperoxy radical (HO2) plays a critical role in Earth's atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work, we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concentrations and vibrational spectra of these complexes. We predict that when the HO2 concentration is on the order of 108molecules·cm-3 at 298 K, that the number of HO2···H2O complexes is on the order of 107molecules·cm-3 and the number of HO2···(H2O)2 complexes is on the order of 106molecules·cm-3. Using the computed abundance of HO2···H2O, we predict that, at 298 K, the bimolecular rate constant for HO2···H2O + HO2 is about 10 times that for HO2 + HO2.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

Potential energy functions for ground state surfaces of HCO and HNO

Analytical potential functions are reported for the ground state surfaces of HCO and HNO, the functions being derived from spectroscopic and ab initio data. Harmonized force fields have been deduced for the stable configurations of both molecules and vibration frequencies predicted for the metastable species COH and NOH.

The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

Exploring the free energy surfaces of clusters using reconnaissance metadynamics

A new approach is proposed for exploring the low-energy structures of small to medium-sized aggregates of atoms and molecules. This approach uses the recently proposed reconnaissance metadynamics method [G. A. Tribello, M. Ceriotti, and M. Parrinello. Proc. Natl. Acad. Sci. U.S.A. 107(41), 17509 (2010)] in tandem with collective variables that describe the average structure of the coordination sphere around the atoms/molecules. We demonstrate this method on both Lennard-Jones and water clusters and show how it is able to quickly find the global minimum in the potential energy surface, while exploring the finite temperature free energy surface. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3628676]

A potential energy surface for the ground state of acetylene, C2H2

A potential energy function has been derived for the ground state surface of C2H2 as a many-body expansion. The 2- and 3-body terms have been obtained by preliminary investigation of the ground state surfaces of CH2( 3B1) and C2H( 2Σ+). A 4-body term has been derived which reproduces the energy, geometry and harmonic force field of C2H2. The potential has a secondary minimum corresponding to the vinylidene structure and the geometry and energy of this are in close agreement with predictions from ab initio calculations. The saddle point for the HCCH-H2CC rearrangement is predicted to lie 2•530 eV above the acetylene minimum.

Analytical functions for the ground state potential surfaces of C3 (X 1 Σ g+) and HCN (X 1 Σ +)

Analytic functions have been obtained to represent the potential energy surfaces of C3 and HCN in their ground electronic states. These functions closely reproduce the available data on the energy, geometry, and force constants in all stable conformations, as well as data on the various dissociation products, and ab initio calculations of the energy at other conformations. The form of the resulting surfaces are portrayed in various ways and discussed briefly.

Potential energy surface intersections in triatomic molecules

The different types of surface intersection which may occur in linear configurations of triatomic molecules are reviewed, particularly with regard to the way in which the degeneracy is split as the molecule bends. The Renner-Teller effect in states of symmetry Π, Δ, Φ, etc., and intersections between Σ and Π, Σ and Δ, and Π and Δ states are discussed. A general method of modelling such intersecting potential surfaces is proposed, as a development of the model previously used by Murrell and Carter and co-workers for single-valued surfaces. Some of the lower energy surfaces of H2O, NH2, O3, C3, and HNO are discussed as examples.

Thermobaric control of gravitational potential energy generation by diapycnal mixing in the deep ocean

Sources and sinks of gravitational potential energy (GPE) play a rate-limiting role in the large scale ocean circulation. A key source is turbulent diapycnal mixing, whereby irre- versible mixing across isoneutral surfaces is enhanced by turbulent straining of these surfaces. This has motivated international observational efforts to map diapycnal mixing in the global ocean. However, in order to accurately relate the GPE supplied to the large scale circulation by diapycnal mixing to the mixing energy source, it is first necessary to determine the ratio, ξ , of the GPE generation rate to the available potential energy dissipation rate associated with turbulent mixing. Here, the link between GPE and hydro- static pressure is used to derive the GPE budget for a com- pressible ocean with a nonlinear equation of state. The role of diapycnal mixing is isolated and from this a global cli- matological distribution of ξ is calculated. It is shown that, for a given source of mixing energy, typically three times as much GPE is generated if the mixing takes place in bottom waters rather than in the pycnocline. This is due to GPE destruction by cabbelling in the pycnocline, as opposed to thermobaric enhancement of GPE generation by diapycnal mixing in the deep ocean.

Tropical deep convection, convective available potential energy and sea surface temperature

The convective available potential energy (CAFE) based on monthly mean sounding has been shown to be relevant to deep convection in the tropics. The variation of CAFE with SST has been found to be similar to the variation of the frequency of deep convection at one station each in the tropical Atlantic and W. Pacific oceans. This suggests a strong link between the frequency of tropical convection and CAFE. It has been shown that CAFE so derived can be interpreted as the work potential of the atmosphere above the boundary layer with ascent in the convective region and subsidence in the surrounding cloud-free region.

Levitation effect and its relationship with the underlying potential energy landscape

Positions of potential energy minima for spherical monatomic sorbates in zeolite NaY have been identified for different sizes of the sorbate. It is found that for small sorbates (sigma less than or equal to 4.96 Angstrom) there are only six adsorption sites per alpha-cage, which are located close to the inner surface of the alpha-cage. For larger sorbates, additional sites of comparable energies appear close to the 12-ring window which forms the bottleneck for intercage diffusion. Minimum energy paths between these sites have been computed. These suggest that the barriers for both intracage and intercage site-to-site migrations are comparable and decrease with increase in sorbate size. Earlier simulation studies on the diffusion of monatomic sorbates in zeolites indicated that there is a dramatic change in the nature of dependence of D on sorbate size around 4.96 Angstrom, for zeolite NaY. Therefore, the present results suggest that the dependence of D on sorbate size and the changes in the potential energy landscape are correlated. The sorbate-zeolite system is characterized by a flatter potential energy landscape when the sorbate size is large. (C) 1999 American Institute of Physics. [S0021-9606(99)51110-0].

Characterization of the dynamics of glass-forming liquids from the properties of the potential energy landscape

We develop a framework for understanding the difference between strong and fragile behavior in the dynamics of glass-forming liquids from the properties of the potential energy landscape. Our approach is based on a master equation description of the activated jump dynamics among the local minima of the potential energy (the so-called inherent structures) that characterize the potential energy landscape of the system. We study the dynamics of a small atomic cluster using this description as well as molecular dynamics simulations and demonstrate the usefulness of our approach for this system. Many of the remarkable features of the complex dynamics of glassy systems emerge from the activated dynamics in the potential energy landscape of the atomic cluster. The dynamics of the system exhibits typical characteristics of a strong supercooled liquid when the system is allowed to explore the full configuration space. This behavior arises because the dynamics is dominated by a few lowest-lying minima of the potential energy and the potential energy barriers between these minima. When the system is constrained to explore only a limited region of the potential energy landscape that excludes the basins of attraction of a few lowest-lying minima, the dynamics is found to exhibit the characteristics of a fragile liquid.