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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Density functional based methods for light harvesting molecules

The goal of the proposal was to computationally study the photoinduced charge transfer excited states of organic molecules. The systems of interest are the large organic supramolecules that have potential for photovoltaic applications. The simulation of the charge transfer excited states in large supramolecular assemblies require quantum mechanical methods that can be applied to systems with hundreds of atoms. Through this project we have implemented a perturbative delta-self-consistent field method that can easily describe the charge transfer excited states with regular density functionals without range separation. The cost of the calculations of an excited state is similar to that of the ground state. The method also allows for calculation of the energy gradients of the excited state. The developed method was applied to study a number of different supramolecular systems containing hundreds of atoms with excellent agreement with experiment. The absorption characteristics and the influence of density functional approximations were also examined. These led to several studies on the variety of organic electron donor and acceptor molecules. Apart from these developments through this project we also improved the code capabilities by implementing new meta-GGA functionals. This was a major step since the code is purely density functional and earlier the functional capabilities were limited only to generalized gradient approximations. A total of 23 peer-reviewed publications in top chemical physics journals resulted from this grant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Analytic gradients for compressed multistate pair-density functional theory

Photochemical reactions often involve states that are closely coupled due to near degeneracies, for example by proximity to conical intersections. Therefore, a multistate method is used to accurately describe these states; for example, ordinary perturbation theory is replaced by quasidegenerate perturbation theory. Multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to approximate the full dynamical correlation energy of strongly correlated systems, and we recently proposed compressed multistate pair-density functional theory (CMS-PDFT) to treat closely coupled states. In the present paper, we report the implementation of analytic gradients for CMS-PDFT in both OpenMolcas and PySCF, and here we illustrate the use of these gradients by applying the method to the excited states of formaldehyde and phenol.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1994

A Doubles Correction to Electronic Excited States from Configuration Interaction in the Space of Single Substitutions

A perturbative correction to the method of configuration interaction with single substitutions (CIS) is presented. This CIS(D) correction approximately introduces the effect of double substitutions which are absent in CIS excited states. CIS(D) is a second-order perturbation expansion of the coupled-cluster excited state method, restricted to single and double substitutions, in a series in which CIS is zeroth order, and the first-order correction vanishes. CIS (D) excitation energies are size consistent and the calculational complexity scales with the fifth power of molecular size, akin to second-order Moller-Plesset theory for the ground state. Calculations on singlet excited states of ethylene, formaldehyde, acetaldehyde, butadiene and benzene show that CIS (D) is a uniform improvement over CIS. CIS(D) appears to be a promising method for examining excited states of large molecules, where more accurate methods are not feasible.

Head-Gordon, Martin↗
DOE OSTI2022

Quadratic Unitary Coupled-Cluster Singles and Doubles Scheme: Efficient Implementation, Benchmark Study, and Formulation of an Extended Version

An efficient implementation of the quadratic unitary coupled-cluster singles and doubles (qUCCSD) scheme for calculations of electronic ground and excited states using an unrestricted molecular spin–orbital formulation and an efficient tensor contraction library is reported. The accuracy of the qUCCSD scheme and the efficiency of the present implementation are demonstrated using extensive benchmark calculations of excitation energies and an application to S o → S 1 vertical excitation energies for cis- and trans-4a,4b-dihydrotriphenylene. The qUCCSD scheme has been shown to provide improved excitation energies compared with the UCC3 scheme formulated based on perturbation theory. Here, a UCC truncation scheme that can provide excitation energies correct through the fourth order is also presented to further improve the accuracy of the qUCCSD scheme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tuning the Dimensionality of Excitons in Colloidal Quantum Dot Molecules

Electrically coupled quantum dots (QDs) can support unique optoelectronic properties arising from the superposition of single-particle excited states. Experimental methods for integrating colloidal QDs within the same nano-object, however, have remained elusive to the rational design. Here, we demonstrate a chemical strategy that allows for the assembling of colloidal QDs into coupled composites, where proximal interactions give rise to unique optoelectronic behavior. The assembly method employing “adhesive” surfactants was used to fabricate both homogeneous (e.g., CdS–CdS, PbS–PbS, CdSe–CdSe) and heterogeneous (e.g., PbS–CdS, CdS–CdSe) nanoparticle assemblies, exhibiting quasi-one-dimensional exciton fine structure. In addition, tunable mixing of single-particle exciton states was achieved for dimer-like assemblies of CdSe/CdS core–shell nanocrystals. The nanoparticle assembly mechanism was explained within the viscoelastic interaction theory adapted for molten-surface colloids. Furthermore, we expect that the present work will provide the synthetic and theoretical foundation needed for building assemblies of many inorganic nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2001

Two-photon or higher-order absorbing optical materials and methods of use

Compositions capable of simultaneous two-photon absorption and higher order absorptivities are disclosed. Many of these compositions are compounds satisfying the formulae D-.PI.-D, A-.PI.-A, D-A-D and A-D-A, wherein D is an electron donor group, A is an electron acceptor group and .PI. comprises a bridge of .pi.-conjugated bonds connecting the electron donor groups and electron acceptor groups. In A-D-A and D-A-D compounds, the .pi. bridge is substituted with electron donor groups and electron acceptor groups, respectively. Also disclosed are methods that generate an electronically excited state of a compound, including those satisfying one of these formulae. The electronically excited state is achieved in a method that includes irradiating the compound with light. Then, the compound is converted to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of light. The sum of the energies of all of the absorbed photons is greater than or equal to the transition energy from a ground state of the compound to the multi-photon excited state. The energy of each absorbed photon is less than the transition energy between the ground state and the lowest single-photon excited state of the compound is less than the transition energy between the multi-photon excited state and the ground state.

Marder, Seth↗
DOE OSTI2026

Accurate energies for ππ* excited states via exchange scaling: the XS-CASSCF method

The state-averaged complete-active space self-consistent field method (SA-CASSCF) is a widely employed electronic structure method used for studying photochemistry and dynamics owing to its ability to provide a reliable description even of complicated cases while still retaining computational efficiency. However, SA-CASSCF suffers from one Achilles heel, related to the description of ionic ππ* excited states, whose energy is often overestimated by 1–2 eV. In light of this challenge, we present the XS-CASSCF method, a new approach based on the idea of exchange scaling (XS) that screens the involved energy terms to improve the excitation energies of singlet ionic ππ* states. First, we illustrate the power of the XS-CASSCF method using hexatriene and para-quinodimethane as examples, showing that it corrects the targeted ionic states while leaving the other states largely unaffected, giving root-mean-square errors (RMSE) below 0.2 eV for the four lowest states in both cases. Subsequently, XS-CASSCF vertical excitation energies are tested against theoretical best estimates for a set of 11 molecules and 56 excited states. XS-CASSCF performs exceptionally well for the ππ* states of hydrocarbons, reducing the RMSE over 21 excitation energies from 0.96 to 0.27 eV. In the challenging subset of molecules with heteroatoms and a larger number of ππ* and nπ* states, we find that improvements can also be obtained, albeit not as pronounced. We conclude with an outlook into more realistic molecular materials focusing on their singlet–triplet (S 1 /T 1 ) gaps, finding that significant improvements can be obtained along the whole range of S 1 /T 1 gaps studied, going from 0.1 eV to more than 1.5 eV. Owing to notable improvements across significant classes of molecules combined with its conceptual simplicity, we believe that XS-CASSCF is a promising addition to the electronic structure toolbox, serving both as a standalone electronic structure method and as a starting point for further correlated treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electronic structure theory with molecular point group symmetries on quantum annealers

Quantum computation has the potential to revolutionize quantum chemistry through major speedups in computation times and an exponential reduction in computational resources. Here, we combine the symmetry-adapted Jordan–Wigner encoding based on the full Boolean symmetry group $\mathbb{Z}$$^{k}_{2}$ with our new implementation of the Xia–Bian–Kais (XBK) method for improving the efficiency of electronic structure theory calculations on quantum annealers, particularly by reducing the number of qubits needed to achieve the same accuracy. By providing a more extensive symmetry-adapted encoding (SAE) than previous work, we are able to simulate molecules larger than those previously reported that have been studied using methods developed for quantum annealers and without using an active space. We calculated the potential energy surfaces of H 2 , LiH, He 2 , H 2 O, O 2 , N 2 , Li 2 , F 2 , CO, BH 3 , NH 3 , and CH 4 , with the largest molecule in the STO-6G basis set requiring 16 qubits with our SAE, and compared them with full configuration interaction results. The application of SAE to the XBK method provides an exponential reduction in the size of the Hilbert space and scales well with the size of the problem. It does not introduce significant additional errors for even or large values of a key variational parameter that determines the number of ancilla qubits used in the XBK method’s Hamiltonian embedding, or for certain molecules such as He 2 and H 2 O. Here, we provide an explanation for this behavior and a recommendation on the usage of our method. In addition, we briefly discuss the potential of extracting electronic excited states from our method.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1986

Accuracy of the energy-corrected sudden (ECS) scaling procedure for rotational excitation of CO by collisions with Ar

The utility of the energy-corrected sudden (ECS) scaling method is evaluated on the basis of how accurately it predicts the entire matrix of state-to-state rate constants, when the fundamental rate constants are independently known. It is shown for the case of Ar-CO collisions at 500 K that when a critical impact parameter is about 1.75-2.0 A, the ECS method yields excellent excited state rates on the average and has an rms error of less than 20 percent.

Green, S.↗
DOE OSTI2026

Preparing Fermions via Classical Sampling and Linear Combinations of Unitaries

We present an extension of the Evolving density matrices on Qubits (E$ρ$OQ) framework that enables efficient fault-tolerant preparation of fermionic quantum states. The original method circumvents state preparation by stochastic sampling, but faces a sign problem in fermionic systems leading to a large number of circuits necessary. We resolve this by combining classical stochastic sampling with a linear combination of unitaries method that avoids the exponential circuit scaling that plagued naïve implementations. The resulting algorithm requires $\mathcal{O}(M^2)$$R_Z$ rotations for circuit preparation, where $M$ is the number of retained basis states. We validate the method for ground and excited states in the Thirring model, including by computing two-point correlation functions relevant to scattering. In this model for fixed accuracy $\varepsilon$, $M$ is found to scale empirically as $M \propto \frac{1}{mg}\log(1/g)\log(1/m)$.

Gustafson, Erik J. [RIACS, Mtn. View] (ORCID:00000↗
DOE OSTI2025

An improved guess for the variational calculation of charge-transfer excitations in large systems

Ab initio quantum-chemical methods that perform well for computing the electronic ground state are not straightforwardly transferable to electronically excited states, particularly in large molecular systems. Wave function theory offers high accuracy, but is often prohibitively expensive. Methods based on time-dependent density functional theory (TD-DFT) are crucially sensitive to the chosen exchange-correlation functional (XCF) parameterization, and system-specific tuning protocols were therefore proposed to address the method's robustness. Methods based on the variational relaxation of the excited-state electron density showcased promising results for the calculation of charge-transfer excitations, but the complex shape of the electronic hypersurface makes convergence to a specific excited state much more difficult than for the ground state when standard variational techniques are applied. We address the latter aspect by providing suitable initial guesses, which we obtain by two separate constrained algorithms. Combined with the squared-gradient minimization algorithm for all-electrons relaxation in a freeze-and-release scheme (FRZ-SGM), we demonstrate that orbital-optimized density functional theory (OO-DFT) calculations can reliably converge to the charge-transfer states of interest even for large molecular systems. We test the FRZ-SGM method on a phenothiazine-anthraquinone CT excitation in a supramolecular Pd(II) coordination cage complex as a function of the cage conformation. This compound has been studied experimentally prior to our work. We compare this freeze-and-release scheme to two XCF reparameterizations, which were recently proposed as low-cost TD-DFT-based alternatives to variational methods. Two dye-semiconductor complexes, which were previously investigated in the context of photovoltaic applications, serve as a second example to investigate the convergence and stability of the FRZ-SGM approach. Our results demonstrate that FRZ-SGM provides reliable convergence for charge-transfer excited states and avoids variational collapse to lower-lying electronic states, whereas time-dependent DFT calculations with an adequate tuning procedure for the range-separation parameter provide a computationally efficient initial estimate of the corresponding energies, with a computational cost comparable to that of configuration-interaction singles (CIS) calculations.

Bogo, Nicola↗
NASA NTRS2000

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

Bridged Compounds/chemistry↗
NASA NTRS1973

Time-of-flight measurements of metastable state lifetimes.

A time-of-flight method for measurement of the lifetime of metastable molecules is described. The method is applicable to a molecular beam that has molecules in several different metastable excited states. As compared to methods used previously, the method has the advantages that it does not require selective excitation or quenching of the different states; moreover, it does not require a determination of the relative populations or velocity distributions of molecules in the excited states.

Kaslow, D. E.↗
DOE OSTI2024

VOTCA: multiscale frameworks for quantum and classical simulations in soft matter

Many physical phenomena in liquids and soft matter are multiscale by nature and can involve processes with quantum and classical degrees of freedom occurring over a vast range of length- and timescales. Examples range from structure formation processes of complex polymers or even polymer blends (Svaneborg & Everaers, 2023) on the classical side to charge and energy transport and conversion processes (Lee et al., 2019) involving explicit electronic and, therefore, quantum information. The Versatile Object-oriented Toolkit for Coarse-graining Applications (VOTCA) provides multiscale frameworks built on a comprehensive set of methods for the development of classical coarse-grained potentials (VOTCA-CSG) as well as state-of-the art excited state electronic structure methods based on density-functional and many-body Green’s function theories, coupled in mixed quantum-classical models and used in kinetic network models (VOTCA-XTP).

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Earth Mover’s Distance as a Metric to Evaluate the Extent of Charge Transfer in Excitations Using Discretized Real-Space Densities

This paper presents a novel theoretical measure, μ EMD , based on the earth mover's distance (EMD), for quantifying the density shift caused by electronic excitations in molecules. As input, the EMD metric uses only the discretized ground- and excited-state electron densities in real space, rendering it compatible with almost all electronic structure methods used to calculate excited states. The EMD metric is compared against other popular theoretical metrics for describing the extent of electron-hole separation in a wide range of excited states (valence, Rydberg, charge transfer, etc.). Further, the results showcase the EMD metric's effectiveness across all excitation types and suggest that it is useful as an additional tool to characterize electronic excitations. The study also reveals that μ EMD can function as a promising diagnostic tool for predicting the failure of pure exchange-correlation functionals. Specifically, we show statistical relationships among the functional-driven errors, the exact exchange content within the functional, and the magnitude of μ EMD values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elucidating the Role of Hydrogen Bonding in the Optical Spectroscopy of the Solvated Green Fluorescent Protein Chromophore: Using Machine Learning to Establish the Importance of High-Level Electronic Structure

Hydrogen bonding interactions with chromophores in chemical and biological environments play a key role in determining their electronic absorption and relaxation processes, which are manifested in their linear and multidimensional optical spectra. For chromophores in the condensed phase, the large number of atoms needed to simulate the environment has traditionally prohibited the use of high-level excited-state electronic structure methods. By leveraging transfer learning, we show how to construct machine-learned models to accurately predict the high-level excitation energies of a chromophore in solution from only 400 high-level calculations. Here, we show that when the electronic excitations of the green fluorescent protein chromophore in water are treated using EOM-CCSD embedded in a DFT description of the solvent the optical spectrum is correctly captured and that this improvement arises from correctly treating the coupling of the electronic transition to electric fields, which leads to a larger response upon hydrogen bonding between the chromophore and water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra

Green’s function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Conventional methods using the Dyson equation or the cumulant expansion are typically based on the GW self-energy approximation. In order to extend this approximation in molecular systems, a non-perturbative real-time coupled-cluster cumulant Green’s function approach has been introduced, where the cumulant is obtained as the solution to a set of coupled first order, non-linear differential equations. This approach naturally includes non-linear corrections to conventional cumulant Green’s function techniques where the cumulant is linear in the GW self-energy. The method yields the spectral function associated with the core Green’s function, which is directly related to the x-ray photoemission spectra (XPS) of molecular systems. The approach also yields very good results for binding energies and satellite excitations. The x-ray absorption spectrum (XAS) is then obtained as a convolution of the core spectral function and an effective one-body absorption spectrum. Here this approach is extended to include the full coupled-cluster-singles (CCS) core Green’s function by including the complete form of the non-linear contributions to the cumulant as well as all single, double, and triple cluster excitations in the CC amplitude equations. This approach naturally builds in orthogonality and shake-up effects analogous to those in the Mahan-Noizeres-de Dominicis edge singularity corrections that enhance the XAS near the edge. Themethod is illustrated for the XPS and XAS of NH 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗