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We introduce and benchmark a systematically improvable route for excited-state calculations, state-specific configuration interaction ($\Delta$CI), \alert{which is a particular realization of multiconfigurational self-consistent field and…

Chemical Physics · Physics 2023-08-31 Fábris Kossoski , Pierre-François Loos

As an approximation to SDSCI [static-dynamic-static (SDS) configuration interaction (CI), a minimal MRCI; Theor. Chem. Acc. 133, 1481 (2014)], SDSPT2 [Mol. Phys. 115, 2696 (2017)] is a CI-like multireference (MR) second-order perturbation…

Chemical Physics · Physics 2024-11-26 Yibo Lei , Yang Guo , Bingbing Suo , Wenjian Liu

We present two efficient and intruder-free methods for treating dynamic correlation on top of general multi-configuration reference wave functions---including such as obtained by the density matrix renormalization group (DMRG) with large…

Chemical Physics · Physics 2016-09-13 Sandeep Sharma , Gerald Knizia , Sheng Guo , Ali Alavi

We report internally contracted relativistic multireference configuration interaction (ic-MRCI), complete active space second-order perturbation (CASPT2), and strongly contracted n-electron valence state perturbation theory (NEVPT2) on the…

Chemical Physics · Physics 2015-12-31 Toru Shiozaki , Wataru Mizukami

UGA-SSMRPT2, the spin-free perturbative analogue of Mukerjee's State-Specific Multireference Coupled Cluster Theory (MkMRCC) is known to be successful for size-extensive and intruder-free construction of dissociation curves. This work…

Chemical Physics · Physics 2026-02-05 Shamik Chanda , Pratyush Bhattacharjya , Avijit Sen , Sangita Sen

We present a stochastic approach to perform strongly contracted n-electron valence state perturbation theory (SC-NEVPT), which only requires one- and two-body reduced density matrices, without introducing approximations. We use this method…

Chemical Physics · Physics 2021-01-05 Nick S. Blunt , Ankit Mahajan , Sandeep Sharma

The computation of excited electronic states with commonly employed (approximate) methods is challenging, typically yielding states of lower quality than the corresponding ground state for a higher computational cost. In this work, we…

Materials Science · Physics 2020-04-01 Nell Karpinski , Pablo Ramos , Michele Pavanello

An efficient perturbational treatment of spin-orbit coupling within the framework of high-level multi-reference techniques has been implemented in the most recent version of the COLUMBUS quantum chemistry package, extending the existing…

An efficient excited state method, named xCDFCI, in the configuration interaction framework, is proposed. xCDFCI extends the unconstrained nonconvex optimization problem in coordinate descent full configuration interaction~(CDFCI) to a…

Chemical Physics · Physics 2023-08-23 Zhe Wang , Zhiyuan Zhang , Jianfeng Lu , Yingzhou Li

A new state specific correlation correction to configuration interaction singles (CIS) excitation energies is preseted using coupled cluster perturbation theory (CCPT). General expressions for CIS-CCPT are derived and expanded explicitly to…

Chemical Physics · Physics 2015-06-19 Jason N. Byrd , Victor F. Lotrich , Rodney J. Bartlett

The computationally expensive evaluation and storage of high-rank reduced density matrices (RDMs) has been the bottleneck in the calculation of dynamic correlation for multireference wave functions in large active spaces. We present a…

Chemical Physics · Physics 2020-01-08 Ankit Mahajan , Nick S. Blunt , Iliya Sabzevari , Sandeep Sharma

We extend our recently-developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to the calculation of excited-state wavefunctions and energies. We…

Strongly Correlated Electrons · Physics 2017-11-22 Adam A. Holmes , C. J. Umrigar , Sandeep Sharma

Accurate yet efficient modeling of chemical systems with pronounced static correlation in their excited states remains a significant challenge in quantum chemistry, as most electronic structure methods that can adequately capture static…

Chemical Physics · Physics 2025-03-07 Sylvia J. Bintrim , Kevin Carter-Fenk

Double excitations in organic molecules have garnered significant interest as a result of their importance in singlet fission and photophysics. These excitations play a crucial role in understanding the photoexcitation processes in…

Chemical Physics · Physics 2025-09-03 Namana Venkatareddy , Victor Ghosh , H. R. Krishnamurthy , Manish Jain

We present an implementation and benchmark of new approximations in multireference algebraic diagrammatic construction theory for simulations of neutral electronic excitations and UV/Vis spectra of strongly correlated molecular systems…

Chemical Physics · Physics 2021-12-02 Ilia M. Mazin , Alexander Yu. Sokolov

Quantum-selected configuration interaction (QSCI) is a novel quantum-classical hybrid algorithm for quantum chemistry calculations. This method identifies electron configurations having large weights for the target state using quantum…

Chemical Physics · Physics 2025-03-31 Soichi Shirai , Shih-Yen Tseng , Hokuto Iwakiri , Takahiro Horiba , Hirotoshi Hirai , Sho Koh

We extend our assessment of the potential of perturbative coupled cluster (CC) expansions for a test set of open-shell atoms and organic radicals to the description of quadruple excitations. Namely, the second- through sixth-order models of…

Chemical Physics · Physics 2016-05-17 Janus J. Eriksen , Devin A. Matthews , Poul Jørgensen , Jürgen Gauss

The multi-reference Coupled Cluster method first proposed by Meller et al (J. Chem. Phys. 1996) has been implemented and tested. Guess values of the amplitudes of the single and double excitations (the ${\hat T}$ operator) on the top of the…

Chemical Physics · Physics 2016-04-11 Emmanuel Giner , Grégoire David , Anthony Scemama , Jean Paul Malrieu

Excited states in molecules can be difficult to investigate and generally require methods that are either computationally expensive or are not universally accurate. Recent research has focused on using higher-energy Slater determinants as…

Chemical Physics · Physics 2023-01-26 Diana-Gabriela Oprea , Hugh G. A. Burton

To expand the existing QUEST database of accurate vertical transition energies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril et al.~\textit{WIREs Comput.~Mol.~Sci.} \textbf{2021}, \textit{11}, e1517}], we have modeled more than 100…

Chemical Physics · Physics 2024-01-26 Pierre-François Loos , Denis Jacquemin
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