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We present a linear-response formulation of density cumulant theory (DCT) that provides a balanced and accurate description of many electronic states simultaneously. In the original DCT formulation, only information about a single…

Chemical Physics · Physics 2018-09-10 Andreas V. Copan , Alexander Yu. Sokolov

In this work, two approaches for simulating X-ray absorption (XA) spectra with the complete active space self-consistent field (CASSCF) linear response (LR) method are introduced. The first approach employs the well-known core-valence…

Chemical Physics · Physics 2022-03-10 Benjamin Helmich-Paris

L-edge X-ray absorption spectra for first-row transition metal complexes are obtained from relativistic equation-of-motion singles and doubles coupled-cluster (EOM-CCSD) calculations that make use of the core-valence separation (CVS)…

The previously proposed ansatz for density cumulant theory that combines orbital-optimization and a parameterization of the 2-electron reduced density matrix cumulant in terms of unitary coupled cluster amplitudes (OUDCT) is carefully…

Chemical Physics · Physics 2020-12-23 Jonathon P. Misiewicz , Justin M. Turney , Henry F. Schaefer , Alexander Yu. Sokolov

We present a new theoretical approach for the simulations of X-ray photoelectron spectra of strongly correlated molecular systems that combines multireference algebraic diagrammatic construction theory (MR-ADC) [J. Chem. Phys., 2018, 149,…

Chemical Physics · Physics 2022-05-31 Carlos E. V. de Moura , Alexander Yu. Sokolov

We present the first application to real molecular systems of the recently proposed linear-response theory for the density-based basis-set correction method [J. Chem. Phys. 158, 234107 (2023)]. We apply this approach to accelerate the…

Chemical Physics · Physics 2024-02-27 Diata Traore , Julien Toulouse , Emmanuel Giner

We report the development and benchmark of multireference algebraic diagrammatic construction theory (MR-ADC) for the simulations of core-excited states and X-ray absorption spectra (XAS). Our work features an implementation that…

Chemical Physics · Physics 2024-01-23 Ilia M. Mazin , Alexander Yu. Sokolov

Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X-ray spectra of first-row transition metal complexes. However, CTM theory has seldom been applied to the simulation of…

Chemical Physics · Physics 2018-03-06 Kaili Zhang , Gregory S. Girolami , Josh Vura-Weis

We continue our work on developing techniques for studying turbulence with spectroscopic data. We show that Doppler-broadened absorption spectral lines, in particularly, saturated absorption lines, can be used within the framework of the…

Astrophysics · Physics 2009-11-13 A. Lazarian , D. Pogosyan

We study the combination of orbital-optimized density cumulant theory and a new parameterization of the reduced density matrices in which the variables are the particle-hole cumulant elements. We call this combination O$\lambda$DCT. We find…

Chemical Physics · Physics 2022-01-12 Jonathon P. Misiewicz , Justin M. Turney , Henry F. Schaefer

Spectroscopy is an indispensable tool in understanding the structures and dynamics of molecular systems. However computational modelling of spectroscopy is challenging due to the exponential scaling of computational complexity with system…

Quantum Physics · Physics 2021-06-22 Chee-Kong Lee , Chang-Yu Hsieh , Shengyu Zhang , Liang Shi

We present the first successful application of the coupled cluster approach to simulate the X-ray absorption (XA) spectrum of liquid water. The system size limitations of standard coupled cluster theory are overcome by employing a newly…

The phenomenon of orbital relaxation upon excitation of core electrons is a major problem in the linear-response treatment of core-hole spectroscopies. Rather than addressing relaxation through direct dynamical correlation of the excited…

Chemical Physics · Physics 2025-03-26 Megan Simons , Devin A. Matthews

State specific orbital optimized density functional theory (OO-DFT) methods like restricted open-shell Kohn-Sham (ROKS) can attain semiquantitative accuracy for predicting X-ray absorption spectra of closed-shell molecules. OO-DFT methods…

Chemical Physics · Physics 2022-06-15 Diptarka Hait , Katherine J. Oosterbaan , Kevin Carter-Fenk , Martin Head-Gordon

X-ray photon correlation spectroscopy (XPCS) allows for the resolution of dynamic processes within a material across a wide range of length and time scales. X-ray speckle visibility spectroscopy (XSVS) is a related method that uses a single…

Numerical Analysis · Mathematics 2023-01-09 Shaswat Mohanty , Christopher B. Cooper , Hui Wang , Mengning Liang , Wei Cai

An improved version of a recently developed stochastic cluster dynamics (SCD) method {[}Marian, J. and Bulatov, V. V., {\it J. Nucl. Mater.} \textbf{415} (2014) 84-95{]} is introduced as an alternative to rate theory (RT) methods for…

Data Structures and Algorithms · Computer Science 2016-05-04 Tuan L. Hoang , Jaime Marian , Vasily V. Bulatov , Peter Hosemann

We demonstrate a technique for obtaining the density of atomic vapor, by doing a fit of the resonant absorption spectrum to a density-matrix model. In order to demonstrate the usefulness of the technique, we apply it to absorption in the…

Atomic Physics · Physics 2017-06-15 Harish Ravi , Mangesh Bhattarai , Vasant Natarajan

Linear response (LR) is an important tool in the computational chemist's toolbox. It is therefore no surprise that the emergence of quantum computers has led to a quantum version, quantum LR (qLR). However, the current quantum era of…

We report a complete implementation of the coupled-cluster method with single, double, and triple excitations (CCSDT) where tensor decompositions are used to reduce its scaling and overall computational costs. For the decomposition of the…

Chemical Physics · Physics 2020-02-20 Michał Lesiuk

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…

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