Article
Chemistry, Physical
Iulia Emilia Brumboiu, Dirk R. Rehn, Andreas Dreuw, Young Min Rhee, Patrick Norman
Summary: This study presents the analytical molecular gradients for core-excited states within the ADC methods up to extended second-order under the CVS approximation. Results on water, formic acid, and benzene reveal interesting properties of the core-excited states, indicating potential implications for studying molecular dynamics in such states.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Antonia Papapostolou, Maximilian Scheurer, Andreas Dreuw, Dirk R. Rehn
Summary: We introduce an open-source responsefun package that utilizes the intermediate state representation (ISR) approach for computing molecular response properties within the algebraic diagrammatic construction (ADC) framework. By employing symbolic mathematics, users can input textbook sum-over-states (SOS) expressions from time-dependent perturbation theory, which are automatically translated into the corresponding symbolic ADC/ISR formulations. Using the adcc module, the specified response property is directly evaluated for calculating excited states with ADC, and the result is provided to the user. With the responsefun package, we conduct the first ADC/ISR calculations of second-order hyperpolarizability tensors and three-photon-absorption matrix elements.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
David Mester, Mihaly Kallay
Summary: This study extends the reduced-cost scheme based on the frozen virtual natural orbital and natural auxiliary function approaches to core excitations. The efficiency of the approximation is evaluated for the second-order algebraic-diagrammatic construction (ADC(2)) method using the core-valence separation (CVS) and density fitting approaches. The results demonstrate significant computational savings with a moderate error, making the approach feasible for larger systems.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Ilia M. Mazin, Alexander Yu Sokolov
Summary: This study presents a new implementation and benchmark of approximations in multireference algebraic diagrammatic construction theory for simulations of neutral electronic excitations and UV/vis spectra of strongly correlated molecular systems. The results demonstrate that the proposed MR-ADC methods outperform third-order single-reference ADC approximation for weakly correlated electronic states and are competitive with equation-of-motion coupled cluster theory results. For states with multireference character, the performance of the MR-ADC methods is similar to that of N-electron valence perturbation theory.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Adem Halil Kulahlioglu, Andreas Dreuw
Summary: The multistate formulation of the quantum Monte Carlo algebraic diagrammatic construction (ADC) method, QMCADC, is presented. QMCADC solves the Hermitian eigenvalue problem of the second-order ADC scheme for the polarization propagator stochastically by combining ADC schemes with projector quantum Monte Carlo. It allows for massively parallel distributed computing and exploits the sparsity of the effective ADC matrix, thereby relaxing memory and processing requirements of ADC methods significantly.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Ilia M. Mazin, Alexander Yu. Sokolov
Summary: We report the development and benchmark of MR-ADC for the simulations of core-excited states and XAS. The implementation incorporates core-valence separation, providing efficient access to high-energy excited states. Benchmark results indicate the accuracy of MR-ADC is similar to that of single-reference ADC theory. MR-ADC methods are promising for the XAS simulations of multireference systems.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Mikael Scott, Dirk R. Rehn, Sonia Coriani, Patrick Norman, Andreas Dreuw
Summary: The calculation of rotatory strengths using the ADC scheme has been successfully implemented, enabling the simulation of ECD spectra up to third order of perturbation theory. The results produced by ADC methods are comparable in accuracy to coupled cluster methods, demonstrating the usefulness of ADC for calculating chiro-optical properties of organic molecules. Additionally, ADC(2) in combination with the polarizable continuum model successfully reproduces the ECD spectrum of the L-epinephrine enantiomer in water, further showcasing the applicability of this approach.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Samragni Banerjee, Alexander Yu. Sokolov
Summary: This study presents the implementation and applications of non-Dyson algebraic diagrammatic construction theory for charged excitations in three-dimensional periodic solids. The method allows for efficient calculations of crystalline excited-state properties, such as band structures and band gaps, and also reports the first-ever calculations of ground-state properties using a periodic implementation of third-order Moller-Plesset perturbation theory.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Erik Rosendahl Kjellgren, Hans Jorgen Aagaard Jensen
Summary: The multi-configurational short-range (sr) density functional theory has been extended to calculate indirect spin-spin coupling constants (SSCCs) for nuclear magnetic resonance spectroscopy. The performance of the new method is compared to other density functional theories, showing that computationally cost-effective srLDA functionals are preferable. In organic compounds, HF-srDFT is the best choice for calculating SSCCs, while CAS-srDFT is needed for fluorine-metals SSCCs.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Review
Chemistry, Physical
Samragni Banerjee, Alexander Yu. Sokolov
Summary: In this Review, the authors discuss the current state of algebraic diagrammatic construction (ADC) theory for simulating charged excitations and its recent developments. They provide an overview of ADC formalism for the one-particle Green's function, including its single- and multireference formulations and extension to periodic systems. The capabilities of ADC methods and their accuracy for calculating a wide range of excited-state properties are also discussed.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Friederike Schneider, Antonia Papapostolou, Jonas Leitner, Dirk R. Rehn, Andreas Dreuw
Summary: The Cotton-Mouton effect was theoretically investigated using a novel computational methodology. The study focused on the electronic contributions to polarizabilities, magnetizabilities, and hypermagnetizabilities. The gauge origin dependence of the computed tensors and methodology were thoroughly investigated and compared to experimental data and other methods.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
J. Leitner, A. L. Dempwolff, A. Dreuw
Summary: Until now, perturbation-theoretical consistent algebraic diagrammatic construction (ADC) schemes up to third order have been developed for the quantum chemical investigation of electronic transitions and excited-state properties. In this study, we derive for the first time a consistent fourth-order ADC(4) scheme using novel techniques of automated equation and code generation. The resulting ADC(4) excitation energies have been benchmarked against high-level reference data, demonstrating their accuracy. These advancements also open new possibilities for highly accurate ADC methods in studying electron-detached and attached states.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Adem Halil Kulahlioglu, Dirk Rehn, Andreas Dreuw
Summary: The quantum Monte Carlo algebraic diagrammatic construction (QMCADC) method solves the eigenvalue problem of the second-order ADC scheme for polarization propagator stochastically within the QMC framework, allowing for massively parallel computations and reducing memory requirements. By exploiting the sparsity of the effective ADC matrix and distributing memory and processing loads to different computing nodes, fast parallel computing resources can be utilized. The method is shown to provide genuine stochastic solutions to the ADC eigenvalue problem with marginal controllable error, accurately calculating the lowest vertical excitation energy of various molecular systems.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Marvin Hoffmann, Andreas Dreuw
Summary: The theoretical methodology based on ADC(n) allows for connecting excited state properties with molecular orbital picture and deriving structure-function relationships, as demonstrated in an analysis of transition dipole moments of low-lying states of anthracene and (1,4,5,8)-tetraazaanthracene.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Andreas Dreuw, Antonia Papapostolou, Adrian L. Dempwolff
Summary: Algebraic diagrammatic construction (ADC) schemes are ab initio methods that can calculate excited electronic states and electron-detached and -attached states. These methods have great potential for molecular applications such as calculating absorption spectra, photoelectron spectra, and electron attachment processes. ADC originates from Green's function or propagator theory, but recent developments heavily rely on intermediate state representation or effective Liouvillian formalisms. The different approaches for calculating excitation energies, ionization potentials, and electron affinities are related and provide a consistent description of these quantities at equivalent theory levels with comparable errors. Most quantum chemical program packages include ADC methods, but the most complete ADC suite of methods can be found in the recent release of Q-Chem.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Stepan A. Ukhanev, Sergei Fedorov, Yuriy Y. Rusakov, Irina L. Rusakova, Leonid B. Krivdin
Summary: In this study, the spin-spin coupling constants of pentafluorobenzene were calculated at five different levels of theory, taking into account various corrections. The results indicated that most corrections had little effect on the long-range couplings, while they were crucial for the one-bond carbon-fluorine coupling constants. Hartree-Fock calculations were found to be unreliable, while DFT methods showed comparable accuracy to wave function-based methods.
MAGNETIC RESONANCE IN CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
Irina L. Rusakova
Summary: This review discusses the common and newly developed methods for quantum chemical modeling of NMR spectra, starting from the fundamentals of the nonrelativistic and relativistic theory of nuclear magnetic resonance parameters.
Article
Chemistry, Physical
Yuriy Yu. Rusakov, Irina L. Rusakova
Summary: This paper demonstrates the performance of the previously suggested property-energy consistent method on the calculation of chemical shifts. The results show that the proposed basis sets can accurately calculate the chemical shifts of hydrogen, carbon, nitrogen, and oxygen.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Irina L. Rusakova, Yuriy Yu. Rusakov, Leonid B. Krivdin
Summary: This paper reviews the theoretical background and fundamental results of computing mercury chemical shifts and spin-spin coupling constants, with a special emphasis on their stereochemical behavior and applications.
MAGNETIC RESONANCE IN CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Yuriy Yu Rusakov, Irina L. Rusakova
Summary: In this paper, new J-oriented basis sets, pecJ-n (n = 1, 2), for phosphorus and silicon, were presented for high-quality correlated calculations of NMR spin-spin coupling constants. These basis sets were generated using a modified version of the property-energy consistent (PEC) method, and were found to be efficient and accurate in a wide range of electronic systems.
Article
Chemistry, Inorganic & Nuclear
Stepan A. Ukhanev, Sergei V. Fedorov, Yuriy Y. Rusakov, Irina L. Rusakova, Leonid B. Krivdin
Summary: All possible fluorine spin-spin coupling constants in a series of 12 fluoro-benzenes were calculated using three different non-empirical formalisms. The most suitable functionals for the calculation of the coupling constants were identified within the DFT formalism, while the most efficient and accurate schemes for different coupling constants were identified within the SOPPA and CCSD formalisms.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Physical
Nikolas P. Benetis, Marketa Paloncyova, Stefan Knippenberg
Summary: The study investigates the embedding of caffeate methyl ester, luteolin, quercetin, o-phenanthroline, and neocuproine in a liquid disordered lipid bilayer through atomistic calculations, explaining their location and orientation as bio-active antioxidants. The phenanthrolines associate strongly with the lipid tail region, while the other compounds are found among the head groups. The simulations show conformational changes of the flavonoids. The study analyzes the influence of the anisotropic environment on the compounds' optical properties using a hybrid quantum mechanics-molecular mechanics scheme, and highlights the importance of mapping molecular interactions in model membranes for biomedical applications relating to different lipid environments.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Multidisciplinary
Lyudmila I. Larina, Alexander I. Albanov, Stanislav N. Zelinskiy, Vadim V. Annenkov, Irina L. Rusakova
Summary: Substituted acrylamides are widely used in organic and medical chemistry, and understanding their electronic structure, spectral properties, and stereochemical transformations is crucial. The structure and stereodynamic behavior of these compounds were studied using dynamic and multinuclear NMR spectroscopy. The results show that acrylamides exist in solution as Z- and E-isomers, with the E-isomer being more prevalent. The experimental values obtained for the activation energy of the isomers range from 15-17 kcal/mol, depending on the stereochemical structure.
MAGNETIC RESONANCE IN CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Irina L. L. Rusakova, Yuriy Yu. Rusakov
Summary: This review summarizes computational studies on the relativistic effects on NMR chemical shifts of light nuclei in molecules containing heavy main group p-block elements. The article discusses relativistic theories and quantum chemical methods for calculating relativistic NMR chemical shifts. The main focus is on the relativistic calculations of NMR shielding constants of popular light nuclei in compounds with heavy p-elements, particularly the effects of 16th and 17th group elements. The article also considers factors influencing the behavior of relativistic effects on the chemical shifts of light atoms, including the stereochemistry of the relativistic heavy atom and the influence of spin-orbit relativistic effects on the vibrational contributions to the shielding constants of light nuclei.
Article
Biochemistry & Molecular Biology
Irina L. Rusakova, Yuriy Yu. Rusakov
Summary: The sensitivity of relativistic corrections to NMR shielding constants to the configuration of angular spaces of the basis sets was investigated using four-component density functional theory. The dependence of relativistic corrections to s of light nuclei on the basis set used on the light spectator atom was found to be similar to the Fermi-contact contribution to the nonrelativistic spin-spin coupling constant. The artificially saturated nonrelativistic J-oriented and s-oriented basis sets provided better accuracy than standard nonrelativistic s-oriented basis sets for calculating relativistic corrections to NMR shielding constants.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Yuriy Yu. Rusakov, Irina L. Rusakova
Summary: New compact pecJ-n (n = 1, 2) basis sets for the selenium atom are developed for quantum-chemical calculations of NMR spin-spin coupling constants involving selenium nuclei. These basis sets provide accuracy comparable to larger basis sets while being more compact, thanks to the property-energy consistent (PEC) method used in their development. The new basis sets were tested on SSCCs calculations of selenium in various molecules, taking into account relativistic, solvent, and vibrational corrections.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Yuriy Yu. Rusakov, Valentin A. Semenov, Irina L. Rusakova
Summary: The basis set issue is crucial for the accuracy of NMR chemical shift calculations. This paper presents the performance of the pecS-n (n = 1, 2) basis sets on a large dataset of H-1 and C-13 chemical shifts of 23 bioactive natural products. Alternative contraction schemes for the basis sets are proposed and evaluated. The study demonstrates that the contracted basis sets do not significantly improve the accuracy.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Irina L. Rusakova, Stepan A. Ukhanev, Yuriy Yu. Rusakov
Summary: This study thoroughly investigates the influence of relativistic effects on 19F NMR chemical shifts in various fluorine compounds containing one or more iodine atoms. The arrangement of iodine atom(s) relative to the fluorine atom was found to strongly affect the magnitude of the relativistic correction to fluorine shielding constant.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Physical
Yuriy Yu. Rusakov, Irina L. L. Rusakova
Summary: The basis sets used in quantum chemical calculations of P-31 NMR chemical shifts have a significant impact on their accuracy. Existing basis sets for phosphorus atom lack flexibility in important angular regions, leading to misassignments in P-31 NMR spectra. This study proposes new pecS-n (n = 1, 2) basis sets that demonstrate high accuracy and are useful in large-scale quantum chemical calculations of P-31 NMR chemical shifts.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Biomaterials
Silvio Osella, Giovanni Granucci, Maurizio Persico, Stefan Knippenberg
Summary: This computational study investigates the photoisomerization mechanism of the azobenzene molecule in a DPPC lipid membrane. The trans-to-cis isomerization is shown to be a slow process controlled by a torsional mechanism due to strong environmental interaction, while the cis-to-trans mechanism occurs rapidly in sub-ps time scale and is governed by a pedal-like mechanism involving weaker environmental interactions and a different potential energy surface geometry.
JOURNAL OF MATERIALS CHEMISTRY B
(2023)