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NASA NTRS1992

Computational studies of metal-metal and metal-ligand interactions

The geometric structure of Cr(CO)6 is optimized at the modified coupled-pair functional (MCPF), single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory (including a perturbational estimate for connected triple excitations), and the force constants for the totally symmetric representation are determined. The geometry of Cr(CO)5 is partially optimized at the MCPF, CCSD and CCSD(T) levels of theory. Comparison with experimental data shows that the CCSD(T) method gives the best results for the structures and force constants, and that remaining errors are probably due to deficiencies in the one-particle basis sets used for CO. A detailed comparison of the properties of free CO is therefore given, at both the MCPF and CCSD/CCSD(T) levels of treatment, using a variety of basis sets. With very large one-particle basis sets, the SSCD(T) method gives excellent results for the bond distance, dipole moment and harmonic frequency of free CO. The total binding energies of Cr(CO)6 and Cr(CO)5 are also determined at the MCPF, CCSD and CCSD(T) levels of theory. The CCSD(T) method gives a much larger total binding energy than either the MCPF or CCSD methods. An analysis of the basis set superposition error (BSSE) at the MCPF level of treatment points out limitations in the one-particle basis used here and in a previous study. Calculations using larger basis sets reduced the BSSE, but the total binding energy of Cr(CO)6 is still significantly smaller than the experimental value, although the first CO bond dissociation energy of Cr(CO)6 is well described. An investigation of 3s3p correlation reveals only a small effect. The remaining discrepancy between the experimental and theoretical total binding energy of Cr(CO)6 is probably due to limitations in the one-particle basis, rather than limitations in the correlation treatment. In particular an additional d function and an f function on each C and O are needed to obtain quantitative results. This is underscored by the fact that even using a very large primitive se (1042 primitive functions contracted to 300 basis functions), the superposition error for the total binding energy of Cr(CO)6 is 22 kcal/mol at the MCPF level of treatment.

Barnes, Leslie A.↗

NASA NTRS1992

The vibrational frequencies of difluoroethyne

Ab initio coupled-cluster calculations with single and double excitations and with a perturbational treatment of connected triple excitations are reported for difluoroethyne using large basis sets. The results for the transbending mode nu-4 are extremely sensitive to electron correlation and basis set effects. The best theoretical and experimental estimates for the fundamental vibrational frequencies are in excellent agreement.

Breidung, Juergen↗

NASA NTRS1992

The structure and energetics of Cr(CO)6 and Cr(CO)5

The geometric structure of Cr(CO)6 is optimized at the modified coupled pair functional (MCPF), single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory (including a perturbational estimate for connected triple excitations), and the force constants for the totally symmetric representation are determined. The geometry of Cr(CO)5 is partially optimized at the MCPF, CCSD, and CCSD(T) levels of theory. Comparison with experimental data shows that the CCSD(T) method gives the best results for the structures and force constants, and that remaining errors are probably due to deficiencies in the one-particle basis sets used for CO. The total binding energies of Cr(CO)6 and Cr(CO)5 are also determined at the MCPF, CCSD, and CCSD(T) levels of theory. The CCSD(T) method gives a much larger total binding energy than either the MCPF or CCSD methods. An analysis of the basis set superposition error (BSSE) at the MCPF level of treatment points out limitations in the one-particle basis used. Calculations using larger basis sets reduce the BSSE, but the total binding energy of Cr(CO)6 is still significantly smaller than the experimental value, although the first CO bond dissociation energy of Cr(CO)6 is well described. An investigation of 3s3p correlation reveals only a small effect. In the largest basis set, the total CO binding energy of Cr(CO)6 is estimated to be 140 kcal/mol at the CCSD(T) level of theory, or about 86 percent of the experimental value. The remaining discrepancy between the experimental and theoretical value is probably due to limitations in the one-particle basis, rather than limitations in the correlation treatment. In particular an additional d function and an f function on each C and O are needed to obtain quantitative results. This is underscored by the fact that even using a very large primitive set (1042 primitive functions contracted to 300 basis functions), the superposition error for the total binding energy of Cr(CO)6 is 22 kcal/mol at the MCPF level of treatment.

Barnes, Leslie A.↗

NASA NTRS1993

Bond length, dipole moment, and harmonic frequency of CO

A detailed comparison of some properties of CO is given, at the modified coupled-pair functional, single and double excitation coupled-cluster (CCSD), and CCSD(T) levels of theory (including a perturbational estimate for connected triple excitations), using a variety of basis sets. With very large one-particle basis sets, the CCSD(T) method gives excellent results for the bond distance, dipole moment, and harmonic frequency of CO. In a (6s 5p 4d 3f 2g 1h) + (1s 1p 1d) basis set, the bond distance is about 0.005a0 too large, the dipole moment about 0.005 a.u. too small, and the frequency about 6/cm too small, when compared with experimental results.

Barnes, Leslie A.↗

NASA NTRS1994

An ab initio study of HCuCO

HCuCO is studied using a large Gaussian basis set at the coupled cluster singles and doubles level of theory, including a perturbational estimate of the connected triples (CCSD(T)). In contrast with CuCO, HCuCO is linear. The Cu-CO bond in HCuCO is significantly stronger than in CuCO. These differences between HCuCO and CuCO are discussed in terms of theCu-H bond polarizing the Cu 4s electron away from the CO.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1994

On the Interaction of CO and NH3 with BH3 and BF3

BH3CO, BF3CO, BH3NH3, and BF3NH3 have been studied using density functional theory (DFT). The computed geometries are in reasonable agreement with experiment. BF3CO is found to be weakly bound. The binding energies of BH3CO, BH3NH3 , and BF3NH3 have also been computed using the coupled cluster singles and doubles level of theory, including a perturbational estimate of the connected triples [CCSD(T)]. These CCSD(T) calculations are performed using correlation consistent polarized-valence triple-zeta basis sets. These are expected to be the most accurate binding energies to date. The DFT binding energies are in good agreement with those obtained at the CCSD(T) level. The bonding is analyzed using the constrained space orbital variation (CSOV) technique. In addition to analyzing the bonding in BH3CO, BH3NH3, and BF3NH3, the CSOV approach is used to study why the bonding in BF3CO is so weak.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1997

Positive Anharmonicities: The Oxonide Anion as an Example

An accurate ab initio quartic force field for the ozonide anion has been determined at the singles and doubles coupled-cluster level of theory that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), using the augmented valence triple-zeta correlation consistent one-particle basis set. Convergence of the harmonic frequencies with respect to the one-particle basis set has been demonstrated by computing quadratic force fields at the CCSD(T) level using augmented valence double-zeta and quadruple-zeta basis sets. Fundamental vibrational frequencies have been determined via second-order ro-vibrational perturbation theory and also using exact variational methods. Agreement is very good, and they both show that the antisymmetric O-O stretch, v 3, possesses a positive anharmonic correction (that is, the fundamental frequency is predicted to be higher in energy than the harmonic frequency). Comparison of the O_3 and O3 quartic force fields shows that the positive anharmonic correction is the result of a particularly large F3333 symmetry internal coordinate force constant. The reasonableness of this force constant has been tested by computing both F33 and F3333 at the CCSD, CCSD(T), and CASPT2 levels of theory. A discussion of known positive anharmonicities for stretching modes is presented.

Lee, Timothy J.↗

DOE OSTI2022

Benchmarking the semi-stochastic CC( P;Q ) approach for singlet–triplet gaps in biradicals

Here, we recently proposed a semi-stochastic approach to converging high-level coupled-cluster (CC) energetics, such as those obtained in the CC calculations with singles, doubles, and triples (CCSDT), in which the deterministic CC(P;Q) framework is merged with the stochastic configuration interaction Quantum Monte Carlo propagations [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)]. In this work, we investigate the ability of the semi-stochastic CC(P;Q) methodology to recover the CCSDT energies of the lowest singlet and triplet states and the corresponding singlet–triplet gaps of biradical systems using methylene, (HFH) − , cyclobutadiene, cyclopentadienyl cation, and trimethylenemethane as examples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1990

Vibrations in small Mg clusters

The equilibrium geometries, binding energies, and harmonic frequencies of Mg3 and Mg4 have been determined using large atomic natural orbital basis sets in conjunction with high levels of electron correlation. The correlation treatments comprise multireference configuration interaction (MRCI), singles and doubles coupled-cluster (CCSD) theory and the CCSD(T) extension that includes a perturbational estimate of connected triple excitations. As with previous studies of small Be clusters, the CCSD(T) method is found to reproduce the MRCI results with a remarkable degree of accuracy and at a fraction of the computational cost. Using the CCSD(T) method, full quartic force fields for Mg3 and Mg4 have been determined and anharmonic analyses have been performed using second-order perturbation theory. Vibration-rotation interaction constants and centrifugal distortion constants have also been determined.

Lee, Timothy J.↗

NASA NTRS1999

The Impact of Surface Boundary Forcing on Simulation of the 1998 Summer Drought Over the US Midwest Using Factor Separation Technique

The factor separation (FS) technique has been utilized to evaluate quantitatively the impact of surface boundary forcings on simulation of the 1988 summer drought over the Midwestern part of the U.S. The four surface boundary forcings used are: (1)Sea Surface Temperature (SST), (2) soil moisture, (3) snow cover, and (4) sea ice. The Goddard Earth Observing System(GEOS) General Circulation Model (GCM) is used to simulate the 1988 U.S. drought. A series of sixteen simulations are performed with climatological and real 1988 surface boundary conditions. The major single and mutual synergistic factors/impacts are analyzed. The results show that SST and soil moisture are the major single pro-drought factors. The couple synergistic effect of SST and soil moisture is the major anti-drought factor. The triple synergistic impact of SST, soil moisture, and snow cover is the strongest pro-drought impact and is, therefore, the main contributor to the generation of the drought. The impact of the snow cover and sea ice anomalies for June 1988 on the drought is significant only when combined with the SST and soil moisture anomalies.

Stein, Uri↗

NASA NTRS1990

Theoretical study of polarizabilities and hyperpolarizabilities of Ne, HF, F(-), and OH(-)

Theoretical calculations are presented for the polarizability parameters through the fourth power of an applied static electric field for Ne and HF and through the second power in the field for the negative ions F(-) and OH(-). Large Gaussian basis sets are employed and electron correlation is incorporated using the modified coupled pair functional (MCPF) method and for Ne and HF using coupled-cluster single- and double-excitation (CCSD) methods with two approaches of including the effect of triple excitations. The MCPF method is found to perform well in relation to the more rigorous CCSD method.

Chong, Delano P.↗

NASA NTRS2001

Theoretical Studies of Possible Synthetic Routes for the High Energy Density Material Td N4: Excited Electronic States

Vertical electronic excitation energies for single states have been computed for the high energy density material (HEDM) Td N4 in order to assess possible synthetic routes that originate from excited electronic states of N2 molecules. Several ab initio theoretical approaches have been used, including complete active space self-consistent field (CASSCF), state averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D)) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD), which is the highest level of theory employed. Standard double zeta polarized (DZP) and triple zeta double polarized (TZ2P) one-particle basis sets were used. The CASSCF calculations are found to overestimate the excitation energies, while the SA-CASSCF approach rectifies this error to some extent, but not completely. The accuracy of the CIS calculations varied depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results are in generally good agreement. Based on the LRCCSD calculations, the lowest six excited singlet states are 9.35(l(sup)T1), 10.01(l(sup)T2), 10.04(1(sup)A2), 10.07(1(sup)E), 10.12(2(sup)T1), and 10.42(2(sup)T2) eV above the ground state, respectively. Comparison of these excited state energies with the energies of possible excited states of N2+N2 fragments, leads us to propose that the most likely synthetic route for Td N4 involving this mechanism arises from combination of two bound quintet states of N2.

Lee, Timothy J.↗

NASA NTRS1996

On the Coupling Between a Supersonic Turbulent Boundary Layer and a Flexible Structure

A mathematical model and a computer code have been developed to fully couple the vibration of an aircraft fuselage panel to the surrounding flow field, turbulent boundary layer and acoustic fluid. The turbulent boundary layer model is derived using a triple decomposition of the flow variables and applying a conditional averaging to the resulting equations. Linearized panel and acoustic equations are used. Results from this model are in good agreement with existing experimental and numerical data. It is shown that in the supersonic regime, full coupling of the flexible panel leads to lower response and radiation from the panel. This is believed to be due to an increase in acoustic damping on the panel in this regime. Increasing the Mach number increases the acoustic damping, which is in agreement with earlier work.

Frendi, Abdelkader↗

DOE OSTI2021

High-level coupled-cluster energetics by Monte Carlo sampling and moment expansions: Further details and comparisons

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC(P;Q) formalism with the stochastic configuration interaction (CI) and CC Quantum Monte Carlo (QMC) propagations. This article extends our initial study [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)], which focused on recovering the energies obtained with the CC method with singles, doubles, and triples (CCSDT) using the information extracted from full CI QMC and CCSDT-MC, to the CIQMC approaches truncated at triples and quadruples. It also reports our first semi-stochastic CC(P;Q) calculations aimed at converging the energies that correspond to the CC method with singles, doubles, triples, and quadruples (CCSDTQ). The ability of the semi-stochastic CC(P;Q) formalism to recover the CCSDT and CCSDTQ energies, even when electronic quasi-degeneracies and triply and quadruply excited clusters become substantial, is illustrated by a few numerical examples, including the F–F bond breaking in F 2 , the automerization of cyclobutadiene, and the double dissociation of the water molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1993

On nonlinear Tollmien-Schlichting/vortex interaction in three-dimensional boundary layers

The instability of an incompressible three-dimensional boundary layer (that is, one with cross-flow) is considered theoretically and computationally in the context of vortex/wave interactions. Specifically the work centers on two low amplitude, lower-branch Tollmien-Schlichting waves which mutually interact to induce a weak longitudinal vortex flow; the vortex motion, in turn, gives rise to significant wave-modulation via wall-shear forcing. The characteristic Reynolds number is taken as a large parameter and, as a consequence, the waves' and the vortex motion are governed primarily by triple-deck theory. The nonlinear interaction is captured by a viscous partial-differential system for the vortex coupled with a pair of amplitude equations for each wave pressure. Three distinct possibilities were found to emerge for the nonlinear behavior of the flow solution downstream - an algebraic finite-distance singularity, far downstream saturation or far-downstream wave-decay (leaving pure vortex flow) - depending on the input conditions, the wave angles, and the size of the cross-flow.

Davis, Dominic A. R.↗

NASA NTRS1994

Influence of cross-flow on nonlinear Tollmien-Schlichting/vortex interaction

The transition of an incompressible three-dimensional boundary layer with strong cross-flow is considered theoretically and computationally in the context of vortex/wave interactions. Specifically the work centers on two lower-branch Tollmien-Schlichting waves which mutually interact nonlinearly to induce a longitudinal vortex flow. The vortex motion in turn gives rise to significant wave modulation via wall-shear forcing. The characteristic Reynolds number is large and, as a consequence, the waves' and the vortex motion are governed primarily by triple deck theory. The nonlinear interaction is captured by a viscous partial-differential system for the vortex coupled with a pair of amplitude equations for each wave pressure. Following analysis and computation over a wide range of parameters, three distinct responses are found to emerge in the nonlinear behavior of the flow solution downstream: an algebraic finite-distance singularity, far-downstream saturation or far-downstream wave decay leaving pure vortex flow. These depend on the input conditions, the wave angles and the size of the cross flow.

Davis, D. A. R.↗

NASA NTRS1994

Symmetry breaking in O4(+): An application of the Brueckner coupled-cluster method

A recent calculation of the antisymmetric stretch frequency for the rectangular structure of quartet O4(+) using the singles and doubles quadratic configuration interaction method with a perturbational estimate of connected triple excitations (QCISD(T)) method gave a value of 3710 cm(exp -1). This anomalous frequency is shown to be a consequence of symmetry breaking effects, which occur even though the QCISD(T) solution derived from a delocalized SCF reference function lies energetically well below the two localized (symmetry-broken) solutions at the equilibrium geometry. The symmetry breaking is almost eliminated at the CCSD level of theory, but the small remaining symmetry breaking effects are magnified at the CCSD(T) level of theory so that the antisymmetric stretch frequency is still significantly in error. The use of the Brueckner coupled cluster method, however, leads to a symmetrical solution which is free of symmetry breaking effects, with an antisymmetric stretch frequency of 1322 cm(exp -1), in good agreement with our earlier calculations using the complete active space self consistent field/complete active space state interaction (CASSCF/CASSI) method.

Barnes, Leslie A.↗

DOE OSTI2024

State-Selective Double Photoionization of Atomic Carbon and Neon

Double photoionization (DPI) allows for a sensitive and direct probe of electron correlation, which governs the structure of all matter. For atoms, much of the work in theory and experiment that informs our fullest understanding of this process has been conducted on helium, and efforts continue to explore many-electron targets with the same level of detail to understand the angular distributions of the ejected electrons in full dimensionality. Expanding on previous results, we consider here the double photoionization of two 2p valence electrons of atomic carbon and neon and explore the possible continuum states that are connected by dipole selection rules to the coupling of the outgoing electrons in 3P, 1D, and 1S initial states of the target atoms. Carbon and neon share these possible symmetries for the coupling of their valence electrons. Results are presented for the energy-sharing single differential cross section (SDCS) and triple differential cross section (TDCS), further elucidating the impact of the initial state symmetry in determining the angular distributions that are impacted by the correlation that drives the DPI process.

Yip, Frank L. (ORCID:000000025409495X)↗