Quantum Mechanical Versus Polarizable Embedding Schemes: A Study of the Xray Absorption Spectra of Aqueous Ammonia and Ammonium.

The X-ray absorption spectra of aqueous ammonia and ammonium are computed using a combination of coupled cluster singles and doubles (CCSD) with different quantum mechanical and molecular mechanical embedding schemes. Specifically, we compare frozen Hartree-Fock (HF) density embedding, polarizable embedding (PE), and polarizable density embedding (PDE). Integrating CCSD with frozen HF density embedding is possible within the CC-in-HF framework, which circumvents the conventional system-size limitations of standard coupled cluster methods.

Understanding X-ray absorption in liquid water using triple excitations in multilevel coupled cluster theory.

X-ray absorption (XA) spectroscopy is an essential experimental tool to investigate the local structure of liquid water. Interpretation of the experiment poses a significant challenge and requires a quantitative theoretical description. High-quality theoretical XA spectra require reliable molecular dynamics simulations and accurate electronic structure calculations.

Particle-Breaking Unrestricted Hartree-Fock Theory for Open Molecular Systems.

We recently introduced the particle-breaking restricted Hartree-Fock (PBRHF) model, a mean-field approach to address the fractional charging of molecules when they interact with an electronic environment. In this paper, we present an extension of the model referred to as particle-breaking unrestricted Hartree-Fock (PBUHF). The unrestricted formulation contains odd-electron states necessary for a realistic description of fractional charging.

Core-ionization spectrum of liquid water.

We present state-of-the-art calculations of the core-ionization spectrum of water. Despite significant progress in procedures developed to mitigate various experimental complications and uncertainties, the experimental determination of ionization energies of solvated species involves several non-trivial steps such as assessing the effect of the surface potential, electrolytes, and finite escape depths of photoelectrons. This provides a motivation to obtain robust theoretical values of the intrinsic bulk ionization energy and the corresponding solvent-induced shift.

Electronic Characterization of Glycolaldehyde: Experimental and Theoretical Insights from the Core- and Valence-Level Spectroscopy.

The core-level electron excitation and ionization spectra of glycolaldehyde have been investigated by photoabsorption and photoemission spectroscopy at both carbon and oxygen -edges; the valence ionization spectra were also recorded by photoelectron spectroscopy in the UV-vis region. The spectra are interpreted by means of ab initio calculations based on the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) and coupled cluster singles, doubles, and perturbative are in good agreement with the experimental results, and many of the observed features are assigned. The photoabsorption spectra are not only dominated by transitions from core-level orbitals to unoccupied π and σ orbitals but also show structures due to Rydberg transitions.

New Implementation of an Equation-of-Motion Coupled-Cluster Damped-Response Framework with Illustrative Applications to Resonant Inelastic X-ray Scattering.

We present an implementation of a damped response framework for calculating resonant inelastic X-ray scattering (RIXS) at the equation-of-motion coupled-cluster singles and doubles (CCSD) and second-order approximate coupled-cluster singles and doubles (CC2) levels of theory in the open-source program . This framework lays the foundation for future extension to higher excitation methods (notably, the coupled-cluster singles and doubles with perturbative triples, CC3) and to multilevel approaches. Our implementation adopts a fully relaxed ground state and different variants of the core-valence separation projection technique to address convergence issues.

Particle-Breaking Hartree-Fock Theory for Open Molecular Systems.

In this work we present the particle-breaking Hartree-Fock (PBHF) model which is a mean-field approach to open molecular systems. The interaction of a system with the environment is parametrized through a particle-breaking term in the molecular Hamiltonian. The PBHF wave function is constructed through an exponential unitary transformation of a Slater determinant with a given number of electrons.

Oscillator Strengths in the Framework of Equation of Motion Multilevel CC3.

We present an efficient implementation of the equation of motion oscillator strengths for the closed-shell multilevel coupled cluster singles and doubles with perturbative triples method (MLCC3) in the electronic structure program . The orbital space is split into an active part treated with CC3 and an inactive part computed at the coupled cluster singles and doubles (CCSD) level of theory. Asymptotically, the CC3 contribution scales as floating-point operations, where is the total number of virtual orbitals while and are the number of active virtual and occupied orbitals, respectively.

Implementation of Occupied and Virtual Edmiston-Ruedenberg Orbitals Using Cholesky Decomposed Integrals.

We present a trust-region optimization of the Edmiston-Ruedenberg orbital localization function. The approach is used to localize both the occupied and the virtual orbitals and is the first demonstration of general virtual orbital localization using the Edmiston-Ruedenberg localization function. In the Edmiston-Ruedenberg approach, the sum of the orbital self-repulsion energies is maximized to obtain the localized orbitals.

Linear-Scaling Implementation of Multilevel Hartree-Fock Theory.

We introduce a new algorithm for the construction of the two-electron contributions to the Fock matrix in multilevel Hartree-Fock (MLHF) theory. In MLHF, the density of an active molecular region is optimized, while the density of an inactive region is fixed. The MLHF equations are solved in a reduced molecular orbital (MO) basis localized to the active region.

Predictions of Pre-edge Features in Time-Resolved Near-Edge X-ray Absorption Fine Structure Spectroscopy from Hole-Hole Tamm-Dancoff-Approximated Density Functional Theory.

Time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy is a powerful technique for studying photochemical reaction dynamics with femtosecond time resolution. In order to avoid ambiguity in TR-NEXAFS spectra from nonadiabatic dynamics simulations, core- and valence-excited states must be evaluated on equal footing and those valence states must also define the potential energy surfaces used in the nonadiabatic dynamics simulation. In this work, we demonstrate that hole-hole Tamm-Dancoff-approximated density functional theory (hh-TDA) is capable of directly simulating TR-NEXAFS spectroscopies.

Combining multilevel Hartree-Fock and multilevel coupled cluster approaches with molecular mechanics: a study of electronic excitations in solutions.

We investigate the coupling of different quantum-embedding approaches with a third molecular-mechanics layer, which can be either polarizable or non-polarizable. In particular, such a coupling is discussed for the multilevel families of methods, in which the system is divided into an active and an inactive orbital space. The computational cost of the resulting three-layer approaches is reduced by treating the long-range interactions at the classical level.

Transient resonant Auger-Meitner spectra of photoexcited thymine.

We present the first investigation of excited state dynamics by resonant Auger-Meitner spectroscopy (also known as resonant Auger spectroscopy) using the nucleobase thymine as an example. Thymine is photoexcited in the UV and probed with X-ray photon energies at and below the oxygen K-edge. After initial photoexcitation to a ππ* excited state, thymine is known to undergo internal conversion to an nπ* excited state with a strong resonance at the oxygen K-edge, red-shifted from the ground state π* resonances of thymine (see our previous study Wolf, et al.

Equation-of-Motion MLCCSD and CCSD-in-HF Oscillator Strengths and Their Application to Core Excitations.

We present an implementation of equation-of-motion oscillator strengths for the multilevel CCSD (MLCCSD) model where CCS is used as the lower level method (CCS/CCSD). In this model, the double excitations of the cluster operator are restricted to an active orbital space, whereas the single excitations are unrestricted. Calculated nitrogen K-edge spectra of adenosine, adenosine triphosphate (ATP), and an ATP-water system are used to demonstrate the performance of the model.

Accelerated multimodel Newton-type algorithms for faster convergence of ground and excited state coupled cluster equations.

We introduce a multimodel approach to solve coupled cluster equations, employing a quasi-Newton algorithm for the ground state and an Olsen algorithm for the excited states. In these algorithms, both of which can be viewed as Newton algorithms, the Jacobian matrix of a lower level coupled cluster model is used in Newton equations associated with the target model. Improvements in convergence then imply savings for sufficiently large molecular systems, since the computational cost of macroiterations scales more steeply with system size than the cost of microiterations.

e 1.0: An open source electronic structure program with emphasis on coupled cluster and multilevel methods.

The e program is an open source electronic structure package with emphasis on coupled cluster and multilevel methods. It includes efficient spin adapted implementations of ground and excited singlet states, as well as equation of motion oscillator strengths, for CCS, CC2, CCSD, and CC3. Furthermore, e provides unique capabilities such as multilevel Hartree-Fock and multilevel CC2, real-time propagation for CCS and CCSD, and efficient CC3 oscillator strengths.

An efficient algorithm for Cholesky decomposition of electron repulsion integrals.

Approximating the electron repulsion integrals using inner projections is a well-established approach to reduce the computational demands of electronic structure calculations. Here, we present a two-step Cholesky decomposition algorithm where only the elements of the Cholesky basis (the pivots) are determined in the pivoting procedure. This allows for improved screening, significantly reducing memory usage and computational cost.