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Related papers: Analytic Computation of Vibrational Circular Dichr…

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We present the first single-reference calculations of the atomic axial tensors (AATs) using wave-function-based methods including dynamic electron correlation effects using second-order M{\o}ller-Plesset perturbation theory (MP2) and…

Chemical Physics · Physics 2024-06-11 Brendan M. Shumberger , T. Daniel Crawford

We present the first analytic-derivative-based formulation of vibrational circular dichroism (VCD) atomic axial tensors for second-order Moller-Plesset (MP2) perturbation theory. We compare our implementation to our recently reported…

Chemical Physics · Physics 2025-01-14 Brendan M. Shumberger , Kirk C. Pearce , T. Daniel Crawford

We present analytic gradients and derivative couplings for the simplest possible multireference configuration interaction method, CIS-1D, an electronic structure ansatz that includes all single excitations and one lone double excitation on…

Chemical Physics · Physics 2021-02-15 Hung-Hsuan Teh , Joseph E. Subotnik

Intensity enhancement in vibrational circular dichroism (VCD) arises in open-shell transition metal complexes from coupling between ground-state vibrational transitions and magnetic dipole-allowed transitions to low-lying excited states…

Chemical Physics · Physics 2025-07-08 Mariia Sapova , Chandan Kumar , Sahar Ashtari-Jafari , Wybren J. Buma , Lucas Visscher

Numerous numerical studies have shown that geminal-based methods are a promising direction to model strongly correlated systems with low computational costs. Several strategies have been introduced to capture the missing dynamical…

Chemical Physics · Physics 2023-03-22 Artur Nowak , Katharina Boguslawski

We introduce single and double particle-hole excitations in the recently revived spin-projected Hartree-Fock. Our motivation is to treat static correlation with spin-projection and recover the residual correlation, mostly dynamic in nature,…

Chemical Physics · Physics 2016-01-20 Takashi Tsuchimochi , Seiichiro Ten-no

We present a simple and efficient method to incorporate anharmonic effects in the vibrational \textcolor{black}{analyses} of molecules within density functional theory (DFT) calculations. This approach is closely related to the traditional…

The analytic gradient theory for both iterative and non-iterative coupled-cluster approximations that include connected quadruple excitations is presented. These methods include, in particular, CCSDT(Q), which is an analog of the well-known…

Chemical Physics · Physics 2025-03-26 Devin A. Matthews

Analytic energy gradients are presented for a variational two-electron reduced-density-matrix-driven complete active space self-consistent field (v2RDM-CASSCF) procedure that employs the density-fitting (DF) approximation to the…

Chemical Physics · Physics 2018-11-29 J. Wayne Mullinax , Evgeny Epifanovsky , Gergely Gidofalvi , A. Eugene DePrince

Electronic circular dichroism (ECD) spectroscopy captures the chiroptical response of molecules, enabling absolute configuration assignment that is vital for enantioselective synthesis and drug design. The practical use of ECD spectra in…

Quantum Physics · Physics 2026-02-04 Amandeep Singh Bhatia , Sabre Kais

We investigate configuration-interaction (CI) calculations on a basis of molecular orbitals generated by preliminary density-functional theory (DFT) calculations. We use this CI/DFT framework to improve the modeling of core-excited states…

Chemical Physics · Physics 2025-09-11 Giorgio Visentin , Francois Mauger

Asymptotics-based configuration-interaction (CI) methods [G. Friesecke and B. D. Goddard, Multiscale Model. Simul. 7, 1876 (2009)] are a class of CI methods for atoms which reproduce, at fixed finite subspace dimension, the exact…

Quantum Physics · Physics 2012-04-06 Christian Mendl , Gero Friesecke

We have extended the origin-invariant length gauge (LG(OI)) approach -- originally developed by Caricato and co-workers for optical rotation (OR) and electronic circular dichroism (ECD) -- to vibrational circular dichroism (VCD). This…

Chemical Physics · Physics 2026-01-06 Brendan M. Shumberger , James R. Cheeseman , Marco Caricato , T. Daniel Crawford

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

Quantum dynamics simulations (QDSs) are one of the most highly anticipated applications of quantum computing. Quantum circuit depth for implementing Hamiltonian simulation algorithms is commonly time dependent so that long time dynamics…

Quantum Physics · Physics 2024-08-29 Linyun Wan , Jie Liu , Zhenyu Li , Jinlong Yang

We present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed…

Chemical Physics · Physics 2026-03-06 Takashi Tsuchimochi

An externally corrected coupled cluster (CC) method, where an adaptive configuration interaction (ACI) wave function provides the external cluster amplitudes, named ACI-CC, is presented. By exploiting the connection between configuration…

Chemical Physics · Physics 2023-09-27 Gustavo J. R. Aroeira , Madeline M. Davis , Justin M. Turney , Henry F. Schaefer

Circular dichroism, arising from interactions with light fields of opposite spin angular momentum, has become a fundamental tool for molecular characterization. Meanwhile, helical dichroism (HD) - the dichroic response to vortex beams…

The vibrational spectra of simple CH$_3^+$-Rg (Rg=He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction (VCI) theory relying on multidimensional potential energy surfaces (PES) obtained from explicitly…

Chemical Physics · Physics 2020-09-14 Jan Meisner , Philipp P. Hallmen , Johannes Kästner , Guntram Rauhut

The purpose of this article is to present theoretical values for the vibrational and rotational g-factors of several diatomic molecules. The calculations have been carried out at the Multi-Configurational Self-Consistent Field (MCSCF) level…

Chemical Physics · Physics 2025-09-24 Anna Thorn Ekstrøm , Stephan P. A. Sauer
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