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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Uncertainty relations, zero point energy and the linear canonical group

The close relationship between the zero point energy, the uncertainty relations, coherent states, squeezed states, and correlated states for one mode is investigated. This group-theoretic perspective enables the parametrization and identification of their multimode generalization. In particular the generalized Schroedinger-Robertson uncertainty relations are analyzed. An elementary method of determining the canonical structure of the generalized correlated states is presented.

Sudarshan, E. C. G.↗
NASA NTRS1978

On the contribution of intramolecular zero point energy to the equation of state of solid H2

Experimental evidence shows that the internal zero-point energy of the H2 molecule exhibits a relatively strong pressure dependence in the solid as well as changing considerably upon condensation. It is shown that these effects contribute about 6% to the total sublimation energy and to the pressure in the solid state. Methods to modify the ab initio isolated pair potential to account for these environmental effects are discussed.

Chandrasekharan, V.↗
NASA NTRS1999

The Atomization Energy of Mg4

The atomization energy of Mg4 is determined using the MP2 and CCSD(T) levels of theory. Basis set incompleteness, basis set extrapolation, and core-valence effects are discussed. Our best atomization energy, including the zero-point energy and scalar relativistic effects, is 24.6+/-1.6 kcal per mol. Our computed and extrapolated values are compared with previous results, where it is observed that our extrapolated MP2 value is good agreement with the MP2-R12 value. The CCSD(T) and MP2 core effects are found to have the opposite signs.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1998

C2 Fragmentation Energy of C60 Revisited: Theory Disagrees with Most Experiments

Following our earlier work on the subject, we have carried out density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) calculations of the dissociation energy of the reaction C60 yields C58 + C2 using polarized basis sets and geometries optimized with DFT methods. The present theoretical results support an electronic fragmentation energy D(sub e) around 10-11 eV in disagreement with most experimental results that place the dissociation energy D(sub o) (including zero point energy) around 7-8 eV. The plausible errors remaining in the theoretical calculations are unlikely to account for this big difference (2-4 eV).

Boese, A. Daniel↗
NASA NTRS1997

The Calculation of Accurate Metal-Ligand Bond Energies

The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

Bauschlicher, Charles W.↗
NASA NTRS1984

Carbon and oxygen isotope fractionation in dense interstellar clouds

It is pointed out that isotope fractionation as a result of chemical reactions is due to the small zero-point energy differences between reactants and products of isotopically distinct species. Only at temperatures near absolute zero does this energy difference become significant. Favorable conditions for isotope fractionation on the considered basis exist in space within dense interstellar clouds. Temperatures of approximately 10 K may occur in these clouds. Under such conditions, ion-molecule reactions have the potential to distribute isotopes of hydrogen, carbon, oxygen unequally among the interstellar molecules. The present investigation makes use of a detailed model of the time-dependent chemistry of dense interstellar clouds to study cosmological isotope fractionation. Attention is given to fractionation chemistry and the calculation of rate parameters, the isotope fractionation results, and a comparison of theoretical results with observational data.

Langer, W. D.↗
NASA NTRS1995

The Heat of Formation of HNO

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO rev. reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X=H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate(DELTA)H(sup o)(sub f) value for HNO using state of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Lee, Timothy J.↗
NASA NTRS1995

The Heat of Formation of HNO

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO reversible reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HNO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X double bond H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate (Delta)H(sub f, sup o) value for HNO using state-of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +/- 0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Lee, Timothy J.↗
NASA NTRS1995

The Dissociation Energies of CH4 and C2H2 Revisited

The bond dissociation energies of CH4 and C2H2 and their fragments are investigated using basis set extrapolations and high levels of correlation. The computed bond dissociation energies (D(sub e)) are accurate to within 0.2 kcal/mol. The agreement with the experimental (D(sub 0)) values is excellent if we assume that the zero-point energy of C2H is 9.18 kcal/mol. The effect of core (1s) correlation on the bond dissociation energies of C-H bonds is shown to vary from 0.2 to 0.7 kcal/mol and that for C-C bonds varies from 0.4 to 2.2 kcal/mol.

Partridge, Harry↗
NASA NTRS1996

The Successive OH Binding Energies of Sc(OH)n+ for n=1-3

The geometries of Sc(OH)n+, for n = 1-3, have been optimized using density functional theory, in conjunction with the B3LYP hybrid functional. The zero-point energies are computed at the same level of theory. The successive OH bond energies have been computed at the CCSD(T) level for ScOH+ and Sc(OH)2+. The computed result for ScOD+ is in excellent agreement with the recent experiment of Armentrout and co-workers. There is a dramatic drop for the third OH, because Sc+ has only two valence electrons and therefore the bonding changes when the third OH is added. The difference between the B3LYP and CCSD(T) OH binding energies for the first two OH groups is discussed.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1976

Equilibrium properties of chemically reacting gases

The equilibrium energy, enthalpy, entropy, specific heat at constant volume and constant pressure, and the equation of state of the gas are all derived for chemically reacting gas mixtures in terms of the compressibility, the mol fractions, the thermodynamic properties of the pure gas components, and the change in zero point energy due to reaction. Results are illustrated for a simple diatomic dissociation reaction and nitrogen is used as an example. Next, a gas mixture resulting from combined diatomic dissociation and atomic ionization reactions is treated and, again, nitrogen is used as an example. A short discussion is given of the additional complexities involved when precise solutions for high-temperature air are desired, including effects caused by NO produced in shuffle reactions and by other trace species formed from CO2, H2O and Ar found in normal air.

Source record↗
NASA NTRS1995

Using Density Functional Theory (DFT) for the Calculation of Atomization Energies

The calculation of atomization energies using density functional theory (DFT), using the B3LYP hybrid functional, is reported. The sensitivity of the atomization energy to basis set is studied and compared with the coupled cluster singles and doubles approach with a perturbational estimate of the triples (CCSD(T)). Merging the B3LYP results with the G2(MP2) approach is also considered. It is found that replacing the geometry optimization and calculation of the zero-point energy by the analogous quantities computed using the B3LYP approach reduces the maximum error in the G2(MP2) approach. In addition to the 55 G2 atomization energies, some results for transition metal containing systems will also be presented.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1984

Energetics of the protonation of CO - Implications for the observation of HOC(+) in dense interstellar clouds

A number of molecular species on the H3CO(+) energy hypersurface is examined. Ab initio molecular orbital theory is used to determine the structures and relative energetics of the two isomers of HCO(+) and HOC(+) together with the affinity of CO for protonation at either end. The proton affinities of H2 and H2CO are also examined. The calculations are performed using large basis sets and include the effects of electron correlation. The calculated vibrational frequencies are used to correct for zero point energy differences. The results show that the proton affinities of H2 and CO to form HOC(+) are within 1 kcal of each other. The calculations demonstrate that there is no thermodynamic driving force to form HOC(+) in collisions of H3(+) with CO, and that the formation of HCO(+) in such collisions is very exoergic. A plausible mechanism is suggested to explain the differences observed between the laboratory and the interstellar medium.

Dixon, D.↗
NASA NTRS2024

Accurate Infrared Line Lists for 20 Isotopologues of CS 2 at Room Temperature

To facilitate atmospheric and spectroscopic studies of carbon disulfide, or CS 2 , in both planetary and exoplanetary atmospheres, we adopt the “Best Theory + Reliable High-resolution Experiment” algorithm to generate semiempirical IR line lists for the 20 most abundant CS 2 isotopologues, denoted as Ames-296K. The IR lists are computed using the Ames-1 potential energy surface, refined using the experimental transition set and an ab initio dipole moment surface fitted from CCSD(T)/aug-cc-pV(T/Q/5+d)Z dipoles extrapolated to a one-particle basis set limit. The IR lists cover the range of 0–10,000 cm -1 , with an S 296K cutoff at 10 -31 cm -1 /molecule·cm -2 (abundance included). A “natural” IR line list at 296 K includes about 10 million lines of the 20 isotopologues, with their intensities scaled by the corresponding abundances. The zero-point energy, partition functions, and abundances are reported for each isotopologue. The energy levels in the global effective Hamiltonian model for 12 C 32 S 2 are adopted to improve the line position accuracy. This new IR list for the main isotopologue is denoted as A+I.296K. Reliable HITRAN2020 line positions are also utilized to improve the accuracy of the 32 S 12 C 34 S, 32 S 12 C 33 S, and 32 S 13 C 32 S isotopologue line lists. The final composite line list is validated against Pacific Northwest National Laboratory experimental cross sections, showing excellent agreement. The agreement supports the quality of the composite line list and the power of synergy between experiment and theory. The new data are proposed for use in updating and expanding the CS 2 data in HITRAN and other high-resolution IR databases. Supplementary files are available in Zenodo and AHED.

Exoplanet atmospheric composition↗
NASA NTRS1993

Theoretical characterization of the reaction NH2 + O yields products

The potential energy surface for NH2+O has been characterized using complete active space self-consistent field (CASSCF)/derivative calculations to determine stationary point geometries and frequencies followed by internally contracted configuration interaction (ICCI) calculations to determine the energetics. The calculations predict a NO bond strength of 85.8 kcal/mol for NH2O. The barrier for isomerization of NH2O to trans-HNOH is predicted to be 48.0 kcal/mol and the barriers for H+HNO forming NH2O and NHOH are predicted to be 2.1 and 8.3 kcal/mol, respectively (all corrected for zero-point energy). The computed heats of formation for NH2O and cis- and trans-HNOH are in good agreement with the present results. The barrier for H + HNO yields H2 + NO is computed to be about 0.3 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1976

Quantum principles and free particles

The quantum principles that establish the energy levels and degeneracies needed to evaluate the partition functions are explored. The uncertainty principle is associated with the dual wave-particle nature of the model used to describe quantized gas particles. The Schroedinger wave equation is presented as a generalization of Maxwell's wave equation; the former applies to all particles while the Maxwell equation applies to the special case of photon particles. The size of the quantum cell in phase space and the representation of momentum as a space derivative operator follow from the uncertainty principle. A consequence of this is that steady-state problems that are space-time dependent for the classical model become only space dependent for the quantum model and are often easier to solve. The partition function is derived for quantized free particles and, at normal conditions, the result is the same as that given by the classical phase integral. The quantum corrections that occur at very low temperatures or high densities are derived. These corrections for the Einstein-Bose gas qualitatively describe the condensation effects that occur in liquid helium, but are unimportant for most practical purposes otherwise. However, the corrections for the Fermi-Dirac gas are important because they quantitatively describe the behavior of high-density conduction electron gases in metals and explain the zero point energy and low specific heat exhibited in this case.

Source record↗
NASA NTRS1994

An Accurate Quartic Force Field and Vibrational Frequencies for HNO and DNO

An accurate ab initio quartic force field for HNO has been determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, CCSD(T), in conjunction with the correlation consistent polarized valence triple zeta (cc-pVTZ) basis set. Improved harmonic frequencies were determined with the cc-pVQZ basis set. Fundamental vibrational frequencies were determined using a second-order perturbation theory analysis and also using variational calculations. The N-0 stretch and bending fundamentals are determined well from both vibrational analyses. The H-N stretch, however, is shown to have an unusually large anharmonic correction, and is not well determined using second-order perturbation theory. The H-N fundamental is well determined from the variational calculations, demonstrating the quality of the ab initio quartic force field. The zero-point energy of HNO that should be used in isodesmic reactions is also discussed.

Dateo, Christopher E.↗
NASA NTRS1994

Heat of Formation of CH2OH

The heat of formation of CH2OH at 298 K is determined to be -15.2 +/- 3.5 kJ/mol using high levels of theory. This is in good agreement with some recent experimental determinations. The assignment of the error bars is discussed in detail and compared with that assigned in previous theoretical calculations. The largest uncertainty arises from the calculation of the zero-point energy.

Bauschlicher, Charles W., Jr.↗