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At least 145 records · Page 8

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NASA NTRS1986

Theoretical dipole moments for the first-row transition metal hydrides

Spectroscopic parameters (D sub e, r sub e, mu) are determined for the first-row transition metal hydrides using better than DZP basis sets at the modified coupled pair functional (MCPF) level. Extensive comparisons between MCPF and complete-active space self-consistent field (CASSCF)/MRCI calculations with natural orbital iterations, and studies with more extensive basis sets, show this level of treatment to supply an accurate and cost-effective treatment of these systems. For the transition metal hydrides, the bonding can arise from either the 3d(n)4s(2) or 3d(n + 1)4s(1) atomic asymptotes, or a mixture of both. Since the dipole moment arising from these two bonding mechanisms is very different, the dipole moment is found to be directly related to the 3d population. Thus, the magnitude of the dipole moments provides a sensitive test of the wave function, and gives insight into the nature of the bonding.

Chong, D. P.↗

NASA NTRS2017

The Failure of Correlation to Describe Out-of-Plane Carbon=Carbon Bending

Carbon-carbon multiply bonded systems are improperly described with standard correlation methods and basis sets. For computations of vibrational modes, the out-of- plane bends can be reported as imaginary at worst or simply too low at best. Utilizing the simplest of aromatic structures (cyclopropenylidene) and various levels of theory, this work diagnoses this known behavior for the first time. A combined 1-particle and n-particle basis set effect conspire to produce these non-physical results. When moving from sp2 to sp3 hybridization in the carbon atoms, the larger number of basis functions overcorrects the energy. This is exacerbated by correlation methods. These allow for occupation of the π and π∗ orbitals in the expanded wave function that combine with the hydrogen s orbitals. As a result, the improperly described space can be further and non-physically stabilized by post-Hartree-Fock correlation. This represents a fundamental problem with at least Hartree-Fock based methods of all flavors in describing carbon. Beyond being a flaw in quantum chemical theory, other repercussions will be present in computations regarding spectroscopy as well as energy and environmental studies where highly-accurate hydrocabon vibrational transitions or thermochemical data are needed.

Fortenberry, Ryan C.↗

NASA NTRS1991

Theoretical study of the low-lying bound states of O2

It is demonstrated that a complete-active-space self-consistent-field (CASSCF) (2p)/MRCI + Q (multireference configuration interaction with a Davidson correction) description in a (13s8p6d 4f2g)/((5s4p3d 2f1g) atomic natural orbits (ANO) basis set supplemented with diffuse functions provides a quantitative description of the six lowest states of O2. The calculated potentials are within 0.05 eV (1.2 kilocal/mol) of accurate experimental results. The importance of substantially expanding the primitive basis set has been investigated, and it is demonstrated that such expansions yield insignificant improvement in the spectroscopic constants. Potential energy curves have also been reported for the weakly bound states of O2. The 5Pi(g) state is estimated to have a D(e) of 0.16 +/- 0.03 eV. The upper bound of D(e) is found to be sufficiently large that the importance of this state as a precursor for the formation of O2 (b 1Sigma(t)(+)) and O(1S) should be reconsidered.

Partridge, Harry↗

NASA NTRS2005

Reliable Spectroscopic Constants for CCH-, NH2- and Their Isotopomers from an Accurate Potential Energy Function

Accurate quartic force fields have been determined for the CCH- and NH2- molecular anions using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, CCSD(T). Very large one-particle basis sets have been used including diffuse functions and up through g-type functions. Correlation of the nitrogen and carbon core electrons has been included, as well as other "small" effects, such as the diagonal Born-Oppenheimer correction, and basis set extrapolation, and corrections for higher-order correlation effects and scalar relativistic effects. Fundamental vibrational frequencies have been computed using standard second-order perturbation theory as well as variational methods. Comparison with the available experimental data is presented and discussed. The implications of our research for the astronomical observation of molecular anions will be discussed.

Lee, Timothy J.↗

DOE OSTI2025

An Ab Initio Electronic Structure Investigation of the Ground and Excited States of ScH + , YH + , and LaH +

Multireference configuration interaction (MRCI), Davidson-corrected MRCI (MRCI+Q), coupled-cluster singles, doubles, and perturbative triples [CCSD(T)], and frozen-core full configuration interaction (fcFCI) calculations were carried out using large, correlation-consistent basis sets to investigate the excited states of the Sc atom and the spin–free and spin–orbit coupled potential energy profiles, energetics, spectroscopic constants, and electron populations of low-lying states of MH + (M = Sc, Y, La). The core electron correlation effects, complete basis set effects, and spin–orbit coupling effects were also evaluated. The first four electronic states of all MH + are 1 2 Δ, 1 2 Σ + , 1 2 Π, and 2 2 Σ + with 1σ 2 1δ 1 , 1σ 2 2σ 1 , 1σ 2 1π 1 , and 1σ 2 3σ 1 single-reference electron configurations, respectively. These states of MH + can be represented by the M 2+ H – ionic structure. The ground states of ScH + , YH + , and LaH + are 1 2 Δ 3/2 , 1 2 Σ + 1/2 , and 1 2 Δ 3/2 with 55.45, 60.54, and 62.34 kcal/mol bond energies, respectively. The core electron correlation was found to be vital for gaining accurate predictions on the ground and excited state properties of MH + . The spin–orbit coupling effects are minor for ScH + but become substantial moving to YH + and LaH + . Overall, the results of this work are in good agreement with the limited set of experimental findings of MH + available in the literature and will be of use for future investigations. Furthermore, the theoretical approaches, findings, and trends reported here are expected to aid studies of similar species.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1989

The dissociation energy of N2

The requirements for very accurate ab initio quantum chemical prediction of dissociation energies are examined using a detailed investigation of the nitrogen molecule. Although agreement with experiment to within 1 kcal/mol is not achieved even with the most elaborate multireference CI (configuration interaction) wave functions and largest basis sets currently feasible, it is possible to obtain agreement to within about 2 kcal/mol, or 1 percent of the dissociation energy. At this level it is necessary to account for core-valence correlation effects and to include up to h-type functions in the basis. The effect of i-type functions, the use of different reference configuration spaces, and basis set superposition error were also investigated. After discussing these results, the remaining sources of error in our best calculations are examined.

Almloef, Jan↗

NASA NTRS1989

The dissociation energy of N2

Almlof, Jan↗

NASA NTRS1991

An ab initio study of the C3(+) cation using multireference methods

The energy difference between the linear 2 sigma(sup +, sub u) and cyclic 2B(sub 2) structures of C3(+) has been investigated using large (5s3p2d1f) basis sets and multireference electron correlation treatments, including complete active space self consistent fields (CASSCF), multireference configuration interaction (MRCI), and averaged coupled-pair functional (ACPF) methods, as well as the single-reference quadratic configuration interaction (QCISD(T)) method. Our best estimate, including a correction for basis set incompleteness, is that the linear form lies above the cyclic from by 5.2(+1.5 to -1.0) kcal/mol. The 2 sigma(sup +, sub u) state is probably not a transition state, but a local minimum. Reliable computation of the cyclic/linear energy difference in C3(+) is extremely demanding of the electron correlation treatment used: of the single-reference methods previously considered, CCSD(T) and QCISD(T) perform best. The MRCI + Q(0.01)/(4s2p1d) energy separation of 1.68 kcal/mol should provide a comparison standard for other electron correlation methods applied to this system.

Taylor, Peter R.↗

NASA NTRS1979

Finite-field Calculations of Molecular Polarizabilities Using Field-Induced Polarization Functions: Second- and Third-order Perturbation Correlation Corrections to the Coupled Hartree-Fock Polarizability of H2O

Ordinary Rayleigh-Schroudinger perturbation theory with Moller-Plesset (RSMP) partitioning is used to calculate second- and third-order correlation corrections to the CHF polarizability and dipole moment of the water molecule by a finite-field procedure. Pade approximants are found to be useful in accelerating the convergence of the property perturbation expansions. Field-induced polarization functions suitable for polarizability calculations are determined. The average polarizability calculated, neglecting vibrational averaging, with Dunning's (9s5p/4s-4s2p/2s) contracted GTO basis set augmented by field-induced lslp2d/lp polarization functions is within 3 per cent of the experimental result. Correlation corrections to the dipole moment and polarizability of the water molecule calculated by the finite-field RSMP and single + double excitation CI(SDCI) methods for the same basis set are found to be in close agreement. The RSMP approach has the advantages of being size-consistent and of being capable of greater efficiency than the SCDI method. Comparative calculations carried out using Epstein-Nesbet partitioning show that through third order RSEN correlation perturbation expansions for the dipole moment and polarizability are less rapidly convergent than RSMP expansions. However, reasonable accord with RSMP results can be achieved by using Pade approximants to accelerate the convergence of RSEN energy perturbation expansions. The convergence of RSMP property correlation expansions based on the zeroth-order uncoupled-Hartree-Fock (UCHF) and coupled-Hartree-Fock (CHF) approximations are compared through third order. Whereas the CHF + RSMP expansions are for practical purposes fully converged, the UCHF + RSMP expansions are not adequately converged.

Langhoff, S. R.↗

NASA NTRS2004

The Bonding of NO2, NH3, and CH2NY to Models of a (10,0) Carbon Nanotube

We have studied the bonding of NO2, NH3, and CH2NH to a (10,O) carbon nanotube using the MP2 and ONIOM methods with extended basis sets. We find bond strengths of 3.5, 3.6. and 6.3 kcal/mol for NO2, NH3, and CH2NH, respectively, using the ONIOM method with the high accuracy part treated at the MP2/aug-CC-pVTZ level and the remainder of the CNT approximated at the UFF level and including an estimate of basis set superposition error using the counterpoise method.

Walch, Stephen P.↗

NASA NTRS1971

Characterization of impulse noise and analysis of its effect upon correlation receivers

A noise model is formulated to describe the impulse noise in many digital systems. A simplified model, which assumes that each noise burst contains a randomly weighted version of the same basic waveform, is used to derive the performance equations for a correlation receiver. The expected number of bit errors per noise burst is expressed as a function of the average signal energy, signal-set correlation coefficient, bit time, noise-weighting-factor variance and probability density function, and a time range function which depends on the crosscorrelation of the signal-set basis functions and the noise waveform. A procedure is established for extending the results for the simplified noise model to the general model. Unlike the performance results for Gaussian noise, it is shown that for impulse noise the error performance is affected by the choice of signal-set basis functions and that Orthogonal signaling is not equivalent to On-Off signaling with the same average energy.

Houts, R. C.↗

NASA NTRS1995

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBRO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

Lee. Timothy J.↗

NASA NTRS1995

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBrO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

Lee, Timothy J.↗

NASA NTRS1980

On the 3d2 4s2, 3d3 4s1, and 3d4 states of Ti

The energies of the 3F (3d2 4s2), 5F (3d3 4s1) and 5D (3d4) states of Ti are investigated on the basis of MCSCF and CI calculations. Following SCF calculations using a basis set including the primitive set of Wachters (1970) and the diffuse d function of Hay (1977), four full-electron CI calculations involving the 3d and 4s electrons were performed to obtain the natural orbitals, and the full CI calculations were repeated. MCSCF calculations then performed using the most important configurations of the natural orbital basis are found to be in agreement with those of Dunning (1980), but to differ from CI results. CI(SD) calculations including single and double excitations from the MCSCF reference are found to be in agreement with the full CI but differ from experimental energy separations. Further calculations reveal that Dunning's MCSCF description is an oversimplication of the problem, and that the 5F-5D separation at the CI(SD) level is in good agreement with experiment for all basis sets but the 3F state is too low relative to the 5F and 5D states.

Bauschlicher, C. W., Jr.↗

NASA NTRS1992

Theoretical study of the bond dissociation energies of methanol

A theoretical study of the bond dissociation energies for H2O and CH3OH is presented. The C-H and O-H bond energies are computed accurately with the modified coupled-pair functional method using a large basis set. For these bonds, an accuracy of +/- 2 kcal/mol is achieved, which is consistent with the C-H and C-C single bond energies of other molecules. The C-O bond is much more difficult to compute accurately because it requires higher levels of correlation treatment and more extensive one-particle basis sets.

Bauschlicher, Charles W., Jr.↗

NASA NTRS2002

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

Dateo, Christopher E.↗

DOE OSTI2025

Toward a Balanced Description of Ground and Excited States with Transcorrelated F12 Methods

By correlating only the 1-particle states occupied in the reference determinant, the conventional design for the single-reference R12/F12 explicitly correlated methods biases them toward the ground-state description, thereby making the treatment of response properties of the ground state, and energies and other properties of excited states less robust. While the use of multireference methods and/or extensions of the standard SP-projected geminals can achieve a more balanced description of ground and excited states, here we show that the same goals can be achieved by extending the action of F12 correlators to the occupied and valence unoccupied 1-particle states only. This design choice reflects the strong dependence of the optimal correlation length scale of the F12 ansatz on the orbital energies/structure, and helps to avoid the unphysical raising of the ground-state energy if the F12 geminals are used to correlate pairs of all 1-particle states. The improved F12 geminal design is incorporated into the unitary transcorrelation framework to produce a unitary 2-body Hamiltonian that incorporates the short-range dynamical correlation physics for ground and low-energy excited states in a balanced manner. This explicitly correlated effective Hamiltonian reduces the basis set requirement on the correlation-consistent basis cardinal number by 1 or more over the uncorrelated counterpart for the description of ground-state coupled-cluster singles and doubles (CCSD) energies, vertical excitation energies, and harmonic vibrational frequencies of equation-of-motion CCSD low-energy excited states.

Hamiltonians↗

NASA NTRS2022

Energy Landscape, and Structural and Spectroscopic Characterization of Diazirine and Its Cyclic Isomers

Identifying new nitrogenated hydrocarbon molecules in the interstellar medium (ISM) is challenging due to the lack of comprehensive spectroscopic data from experiments. In this computational work, we focus on investigating the structures, relative energies, spectroscopic constants, and energy landscape of the cyclic isomers of diazirine (c-CH2N2) using ab initio quantum chemical methods. Density functional theory (DFT) methods and coupled cluster theory with singles and doubles including perturbative triples [CCSD(T)] and CCSD(T) with the explicitly correlated F12 b correction [CCSD(T)-F12b] were employed for this purpose along with large correlation consistent cc-pVTZ, cc-pVQZ, and cc-pV5Z basis sets. Harmonic vibrational frequencies, infrared vibrational intensities, rotational constants, and dipole moments are reported. An harmonic vibrational fundamentals along with centrifugal distortion constants, and vibration-rotation interaction constants are also reported for all the cyclic isomers. The energies computed with the CCSD(T) and CCSD(T)-F12b methods were extrapolated to the one-particle complete basis set (CBS) limit following a three-point formula. At the CCSD(T)-F12b/CBS level of theory the 3,3H-diazirine (c-CH2N2) is the lowest energy cyclic isomer followed by 1,3H-diazirine, (E)-1,2H-Diazirine, and (Z)-1,2H-diazirine which are 20.1, 47.8, and 51.3kcal mol-1above the 3,3H-Diazirine, respectively. Accurate structures and spectroscopic constants that are reported here could be useful for future identification of these cyclic nitrogenated organic molecules in the interstellar medium or circumstellar disks.

Energy Landscape↗