Modified potential energy mass representations for frequency prediction
Modified potential energy mass representations for frequency prediction
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An Ab Initio Based Potential Energy Surface for Water
We report a new determination of the water potential energy surface. A high quality ab initio potential energy surface (PES) and dipole moment function of water have been computed. This PES is empirically adjusted to improve the agreement between the computed line positions and those from the HITRAN 92 data base. The adjustment is small, nonetheless including an estimate of core (oxygen 1s) electron correlation greatly improves the agreement with experiment. Of the 27,245 assigned transitions in the HITRAN 92 data base for H2(O-16), the overall root mean square (rms) deviation between the computed and observed line positions is 0.125/cm. However the deviations do not correspond to a normal distribution: 69% of the lines have errors less than 0.05/cm. Overall, the agreement between the line intensities computed in the present work and those contained in the data base is quite good, however there are a significant number of line strengths which differ greatly.
Partridge, Harry↗
Radiative Heating Rates Computed With Clouds Derived From Satellite‐Based Passive and Active Sensors and their Effects on Generation of Available Potential Energy
Radiative heating rates computed with cloud properties derived from passive and active sensors are investigated. Zonal monthly radiative heating rate anomalies computed using both active and passive sensors show that larger variability in longwave cooling exists near the tropical tropopause and near the top of the boundary layer between ~50°N to ~50°S. Aerosol variability contributes to increases in shortwave heating rate variability. When zonal monthly mean cloud effects on the radiative heating rate computed with both active and passive sensors and those computed with passive sensor only are compared, the latter shows cooling and heating peaks corresponding to cloud top and base height ranges used for separating cloud types. The difference of these two sets of cloud radiative effect on heating rates in the middle to upper troposphere is larger than the radiative heating rate uncertainty estimated based on the difference of two active sensor radiative heating rate profile data products. In addition, radiative heating rate contribution to generation of eddy available potential energy is also investigated. Although radiation contribution to generation of eddy available potential energy averaged over a year and the entire globe is small, radiation increases the eddy available potential energy in the northern hemisphere during summer. Two key elements that longwave radiation contribute to the generation of eddy potential energy are (1) longitudinal temperature gradient in the atmosphere associated with land and ocean surface temperatures contrasts and absorption of longwave radiation emitted by the surface and (2) cooling near the cloud top of stratocumulus clouds.
Kato, Seiji↗
Seasonal variation of radiance variances from satellite observations Implication of seasonal variation of available potential energy in the stratosphere
Nimbus 5 satellite radiances for the period 1973-74 are used to examine the seasonal variation of available potential energy in the stratosphere in order to provide a further observational basis for a long-term numerical simulation of stratospheric circulation. The maximum value of stratospheric zonal available potential energy, A(Z), in the upper and middle stratosphere shows pronounced variations between winter and summer, while little variation occurs in the lower stratospheric A(Z). The aperiodic occurrence of sudden warmings complicates the seasonal variation of A(Z) and A(E) (eddy available potential energy) in the stratosphere, making the energetics irregular. Time-Fourier analysis reveals that the primary variation of A(Z) and A(E) in the stratosphere is annual and semiannual, respectively.
Chen, T.-C.↗
Ab Initio Potential Energy Surface for H-H2
Ab initio calculations employing large basis sets are performed to determine an accurate potential energy surface for H-H2 interactions for a broad range of separation distances. At large distances, the spherically averaged potential determined from the calculated energies agrees well with the corresponding results determined from dispersion coefficients; the van der Waals well depth is predicted to be 75 +/- 3 micro E(h). Large basis sets have also been applied to reexamine the accuracy of theoretical repulsive potential energy surfaces (25-70 kcal/mol above the H-H2 asymptote) at small interatomic separations; the Boothroyd, Keogh, Martin, and Peterson (BKMP) potential energy surface is found to agree with results of the present calculations within the expected uncertainty (+/- 1 kcal/mol) of the fit. Multipolar expansions of the computed H-H2 potential energy surface are reported for four internuclear separation distances (1.2, 1.401, 1.449, and 1.7a(0)) of the hydrogen molecule. The differential elastic scattering cross section calculated from the present results is compared with the measurements from a crossed beam experiment.
Patridge, Harry↗
Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces
Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F+H2 yields HF+H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.
Bauschlicher, Charles W., Jr.↗
Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces
Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F + H2 yields HF + H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.
Bauschlicher, Charles W., Jr.↗
Computed potential energy surfaces for chemical reactions
The objective was to obtain accurate potential energy surfaces (PES's) for a number of reactions which are important in the H/N/O combustion process. The interest in this is centered around the design of the SCRAM jet engine for the National Aerospace Plane (NASP), which was envisioned as an air-breathing hydrogen-burning vehicle capable of reaching velocities as large as Mach 25. Preliminary studies indicated that the supersonic flow in the combustor region of the scram jet engine required accurate reaction rate data for reactions in the H/N/O system, some of which was not readily available from experiment. The most important class of combustion reactions from the standpoint of the NASP project are radical recombinaton reactions, since these reactions result in most of the heat release in the combustion process. Theoretical characterizations of the potential energy surfaces for these reactions are presented and discussed.
Walch, Stephen P.↗
Ab initio projected-unrestricted Hartree-Fock calculation of some potential energy curves for carbonyl fluoride
Some potential energy curves for CF2O were calculated using projected-unrestricted Hartree-Fock (PUHF) theory. The calculations employed a contracted (4s 3p) Gaussian-type atomic orbital basis set. Bound states were found for the X-tilde 1A1 and 1,3A2 states while the 1,3B1 and 1,3B2 states were repulsive in the valence representation. The merits of the PUHF treatment for excited states are discussed. The results are discussed in terms of available experimental information and previous calculations with particular emphasis on the question of the photolysis channels open in the solar spectral region.
Brewer, D. A.↗
Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions
Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.
Walch, Stephen P.↗
Rotational Energy Transfer of N2 Gas Determined Using a New Ab Initio Potential Energy Surface
Rotational energy transfer between two N2 molecules is a fundamental process of some importance. Exchange is expected to play a role, but its importance is somewhat uncertain. Rotational energy transfer cross sections of N2 also have applications in many other fields including modeling of aerodynamic flows, laser operations, and linewidth analysis in nonintrusive laser diagnostics. A number of N2-N2 rigid rotor potential energy surface (PES) has been reported in the literature.
Huo, Winifred M.↗
Computed potential energy surfaces for chemical reactions
Quantum mechanical methods have been used to compute potential energy surfaces for chemical reactions. The reactions studied were among those believed to be important to the NASP and HSR programs and included the recombination of two H atoms with several different third bodies; the reactions in the thermal Zeldovich mechanism; the reactions of H atom with O2, N2, and NO; reactions involved in the thermal De-NO(x) process; and the reaction of CH(squared Pi) with N2 (leading to 'prompt NO'). These potential energy surfaces have been used to compute reaction rate constants and rates of unimolecular decomposition. An additional application was the calculation of transport properties of gases using a semiclassical approximation (and in the case of interactions involving hydrogen inclusion of quantum mechanical effects).
Walch, Stephen P.↗
Numerical calculation of potential-energy curves by the Rydberg-Klein-Rees method.
Potential energy curves for bound states of diatomic molecules from spectroscopic constants, using Rydberg-Klein-Rees method
DIATOMIC MOLECULE↗
Ab initio Potential Energy Surface for H-H2
Ab initio calculations employing large basis sets are performed to determine an accurate potential energy surface for H-H2 interactions for a broad range of separation distances. At large distances, the spherically averaged potential determined from the calculated energies agrees well with the corresponding results determined from dispersion coefficients; the van der Waals well depth is predicted to be 75 +/- (mu)E(sub h). Large basis sets have also been applied to reexamine the accuracy of theoretical repulsive potential energy surfaces. Multipolar expansions of the computed H-H2 potential energy surface are reported for four internuclear separation distances (1.2, 1.401, 1.449, and 1.7a(sub 0) of the hydrogen molecule. The differential elastic scattering cross section calculated from the present results is compared with the measurements from a crossed beam experiment.
Partridge, Harry↗
Quantum Mechanical Determination of Potential Energy Surfaces for TiO and H2O
We discuss current ab initio methods for determining potential energy surfaces, in relation to the TiO and H2O molecules, both of which make important contributions to the opacity of oxygen-rich stars. For the TiO molecule we discuss the determination of the radiative lifetimes of the excited states and band oscillator strengths for both the triplet and singlet band systems. While the theoretical radiative lifetimes for TiO agree well with recent measurements, the band oscillator strengths differ significantly from those currently employed in opacity calculations. For the H2O molecule we discuss the current results for the potential energy and dipole moment ground state surfaces generated at NASA Ames. We show that it is necessary to account for such effects as core-valence Correlation energy to generate a PES of near spectroscopic accuracy. We also describe how we solve the ro-vibrational problem to obtain the line positions and intensities that are needed for opacity sampling.
Langhoff, Stephen R.↗
Potential Energy Curves and Transport Properties for the Interaction of He with Other Ground-state Atoms
The interactions of a He atom with a heavier atom are examined for 26 different elements, which are consecutive members selected from three rows (Li - Ne, Na - Ar, and K,Ca, Ga - Kr) and column 12 (Zn,Cd) of the periodic table. Interaction energies are determined wing high-quality ab initio calculations for the states of the molecule that would be formed from each pair of atoms in their ground states. Potential energies are tabulated for a broad range of Interatomic separation distances. The results show, for example, that the energy of an alkali interaction at small separations is nearly the same as that of a rare-gas interaction with the same electron configuration for the dosed shells. Furthermore, the repulsive-range parameter for this region is very short compared to its length for the repulsion dominated by the alkali-valence electron at large separations (beyond about 3-4 a(sub 0)). The potential energies in the region of the van der Waals minimum agree well with the most accurate results available. The ab initio energies are applied to calculate scattering cross sections and obtain the collision integrals that are needed to determine transport properties to second order. The theoretical values of Li-He total scattering cross sections and the rare-gas atom-He transport properties agree well (to within about 1%) with the corresponding measured data. Effective potential energies are constructed from the ab initio energies; the results have been shown to reproduce known transport data and can be readily applied to predict unknown transport properties for like-atom interactions.
Partridge, Harry↗
RELATIONS AMONG POTENTIAL ENERGY CURVES OF DIATOMIC MOLECULES
Relations among potential energy curves of diatomic molecules - quantum mechanics
ENERGY LEVEL↗
Quantum-mechanical potential-energy curve for the lowest super 1 sigma sub u plus state of He sub 2.
Quantum mechanical potential energy curve of lowest normal state of diatomic helium computed in valence bond scheme, using 17-term wave function of Slater orbitals
ENERGY LEVEL↗