Article
Optics
Meng Zhang, Deheng Shi
Summary: This study calculated the potential energy curves and transition dipole moments between different states of PO+ using various methods, taking into account core-valence correlation, scalar relativistic corrections, and spin-orbit coupling. The results showed variations in the radiative lifetimes and intensities of different transitions, providing useful guidelines for detection in future experiments.
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER
(2021)
Article
Chemistry, Multidisciplinary
Xin Zhang, Liu Leo Liu
Summary: In this study, a novel free N-aluminylene, carbazolylaluminylene 2b, was synthesized and characterized. The coordination behavior of 2b towards transition metal centers was investigated, revealing diverse coordination modes and the ability to modulate electronic properties without changing coordinated atoms. Furthermore, an unprecedented aluminylene-alumanyl transformation was observed, leading to the formation of a rare terminal Cu-alumanyl complex 8. The electronic structures of these complexes and the mechanism of transformation were studied through density functional theory calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiaolong Li, Lorenzo Spada, Silvia Alessandrini, Yang Zheng, Kevin Gregor Lengsfeld, Jens-Uwe Grabow, Gang Feng, Cristina Puzzarini, Vincenzo Barone
Summary: The 1:1 benzofuran-formaldehyde complex was chosen as a model system to analyze pi ->pi* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. The study revealed the dominant role of pi ->pi* interactions in tuning intermolecular interactions, with stacked isomers being more stable than those linked by hydrogen bond or lone-pair ->pi interactions. The experimental detection of only one species confirmed the expectation of effective relaxation to the global minimum under the given conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Soichiro Kyushin, Yuya Suzuki
Summary: This study analyzed the UV/Vis and fluorescence spectra of 9,10-bis(diisopropylsilyl)anthracene through theoretical calculations. It revealed that the cooperation between the silyl groups and anthracene extended the pi conjugation of anthracene, resulting in increased molecular extinction coefficient and fluorescence quantum yield.
Article
Chemistry, Multidisciplinary
Rui Wang, Yingjie Li, Ajun Tang, Yunpeng Li, Hongxiang Li
Summary: The single molecular conductance of viologen derivative VSMe and supramolecular compound VSMe-PA[5] was studied, revealing the gating effect of cation-pi interaction. Theoretical calculations indicated that the higher conductance of VSMe-PA[5] resulted from the planar structure of VSMe and the narrowed HOMO-LUMO bandgap of VSMe-PA[5], which was attributed to the cation-pi interaction between VSMe and PA[5] components.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Samira Gholami, Mohammad Aarabi, Slawomir J. Grabowski
Summary: MP2/aug-cc-pVTZ calculations were performed on systems containing a proton or a lithium cation located between two pi-electron systems or between pi-electron and sigma-electron units. The nature of interactions between these systems, including whether they can be classified as hydrogen or lithium bonds, was discussed. The properties of the interactions with the proton and with the lithium cation in the analyzed complexes were described using the Electron Localization Function and the Natural Bond Orbital approaches.
Article
Chemistry, Multidisciplinary
Yanbo Mei, Xiaodan Chen, Rui Wei, Xiao-Yong Chang, Lizhi Tao, Liu Leo Liu
Summary: This study reports the synthesis, isolation, and characterization of a radical anion with Si and P. The species features a perfectly planar Si2P2 four-membered ring, making it the first Si- and P-containing analog of a bicyclo[1.1.0]butane radical anion. The bonding motif of this unusual species was investigated using experimental and computational methods, revealing the presence of a 2-center-3-electron pi bond between the bridgehead P atoms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Nyancy Halder, Raja Naryanasamy, Dandamudi Usharani, Harapriya Rath
Summary: The chemical conversion of non-aromatic trans-doubly N-confused porphodimethenes to new variants of doubly N-confused porphyrinoids/isophlorinoids has been achieved by manipulating the types of oxidants, the types of meso-aryl substituents, and the number of heterocyclic rings in porphodimethene(s). This conversion leads to the formation of 18 pi aromatic doubly N-confused monooxo porphyrinoids, 16 pi antiaromatic doubly N-confused diioxo porphyrinoids, and sigma-aromatic doubly N-confused tetraoxo isophlorinoids.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Na Liu, Qingzhong Li
Summary: The carbon bond interactions in complexes involving metal halides have been explored, showing that the halogen atom of metal halide can engage in either σ-hole interaction with TH3F or π-hole interaction with F2CO, resulting in different carbon bond structures.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2021)
Article
Chemistry, Applied
Md Hasanul Haque, Honglae Sohn
Summary: In this study, we synthesized and characterized novel pi-sigma* conjugated 1,4-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl)benzene nanoaggregates with aggregation-induced emission enhancement (AIEE) property for the detection of nitroaromatic compounds. The pi-sigma* conjugated nanoaggregates showed excellent sensitivity for sensing explosives.
Article
Chemistry, Inorganic & Nuclear
William J. Pietro, A. B. P. Lever
Summary: Using density functional theory, this study investigated the properties of [(N-2)(RuL5)-L-II](n+) species and derived the characteristics of the Ru-N-2 bond. The ligand electrochemical parameter theory was used to correlate the data, allowing for the design of molecules with desired properties. The research provides a method for predicting the metrics of different systems based on their electron richness and establishes a general approach for ligand design.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Robin N. Perutz, Sylviane Sabo-Etienne, Andrew S. Weller
Summary: This article introduces the concept of sigma-CAM and a new approach to reaction mechanisms. It focuses on the characteristics and dynamic rearrangements of sigma-bond complexes, providing examples of the sigma-CAM mechanism supported by experimental and computational evidence. The authors also critically compare alternative mechanisms for metathesis of metal-element bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Erik T. Ouellette, Ambre Carpentier, I. Joseph Brackbill, Trevor D. Lohrey, Iskander Douair, Laurent Maron, Robert G. Bergman, John Arnold
Summary: Salt metathesis reactions between a low-valent rhenium(I) complex and a series of amidinate-supported tetrylenes led to the formation of rhenium metallotetrylenes with varying extents of Re-E multiple bonding. Temperature played a crucial role in the reactions, leading to isolation of unusual products under different conditions, reflecting the complexity of these metal complexes. Bonding interactions within these complexes were discussed through various spectroscopic, structural, and computational investigations.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Tatsunari Akiyama, Yusuke Tanaka, Ryo Okamoto, Yasuhiro Kajihara, Masayuki Izumi
Summary: This study presents a new method for synthesizing ubiquitinated proteins through delta-selenolysine-mediated isopeptide bond formation. This method allows the synthesis of complex ubiquitinated protein probes, which holds promise for advancing our understanding of ubiquitin biology.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zeqi Jiang, Sheng-Li Niu, Qiang Zeng, Qin Ouyang, Ying-Chun Chen, Qing Xiao
Summary: A novel Pd-catalyzed reaction has been developed for selective alkynylallylation of specific C-C sigma bonds in cyclopropenes, providing an efficient approach to highly functionalized dienynes. The reaction features fascinating atom and step economy and can produce gram-scale products using a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations suggest that the success of the reaction relies on the selective insertion of cyclopropene double bonds into the C-Pd bond of ambidentate Pd complex and subsequent nonclassical beta-C elimination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Carlos E. de Moura, Alexander Yu Sokolov
Summary: We present a new theoretical approach for simulating X-ray photoelectron spectra of strongly correlated molecular systems, which combines multireference algebraic diagrammatic construction theory with a core-valence separation technique. The results demonstrate that this approach is more accurate and reliable for systems with a multireference character and has a low computational cost.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Terrence L. Stahl, Samragni Banerjee, Alexander Yu. Sokolov
Summary: The ADC theory is an accurate and computationally efficient method for simulating electronic excitations in chemical systems. This study benchmarks the accuracy of ADC methods for electron attachment and ionization in open-shell molecules with unrestricted Hartree-Fock reference orbitals and proposes an approach to quantify the spin contamination in charged excited states. The results show that the spin contamination can be reduced by combining EA/IP-ADC with reference orbitals from restricted open-shell Hartree-Fock or orbital-optimized Moller-Plesset perturbation theories.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Rajat Majumder, Alexander Yu. Sokolov
Summary: We have implemented spin-orbit coupling effects in fully internally contracted second-order quasidegenerate N-electron valence perturbation theory (SO-QDNEVPT2) for the first time. This approach combines the description of static electron correlation with an efficient treatment of dynamic correlation and spin-orbit coupling, allowing for accurate computations of ground- and excited-state energies and oscillator strengths. Moreover, we have also developed a simplified approach based on the spin-orbit mean-field approximation (SOMF-QDNEVPT2). The accuracy of both methods has been tested for various systems and found to be in good agreement with experimental and theoretical data.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Jamey K. K. Bower, Maxwell S. S. Reese, Ilia M. M. Mazin, Lina M. M. Zarnitsa, Andrew D. D. Cypcar, Curtis E. E. Moore, Alexander Yu. Sokolov, Shiyu Zhang
Summary: High-valent metal oxo complexes are important intermediates for the activation and hydroxylation of alkyl C-H bonds. In this study, an isolated copper(iii) cyanide complex and its C-H cyanation reactivity were reported. The redox potential of the substrates was found to be a key factor in determining the rate of proton-coupled electron transfer (PCET) reactions, suggesting an oxidative asynchronous mechanism. Based on this mechanistic insight, the copper(iii) cyanide complex demonstrated high selectivity for the cyanation of amines.
Correction
Chemistry, Physical
Samragni Banerjee, Alexander Yu. Sokolov
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Gleb Penyazkov, Sergey D. Prosnyak, Anatoly E. Barzakh, Leonid V. Skripnikov
Summary: The electronic factors for field and mass isotope shifts in various transitions of neutral thallium were calculated using the high-order relativistic coupled cluster approach. These factors were then used to reinterpret previous experimental isotope shift measurements and determine charge radii of different thallium isotopes. Theoretical and experimental results demonstrated good agreement in certain transitions, and it was shown that the specific mass shift factor in a particular transition is significant. The achieved accuracy in estimating charge radii uncertainties allows for a more reliable comparison of charge radii trends in the lead region.
JOURNAL OF CHEMICAL PHYSICS
(2023)
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
Savini Bandaranayake, Ananya Patnaik, Emily Hruska, Quansong Zhu, Alexander Yu. Sokolov, L. Robert Baker
Summary: CuO is commonly used as a photocathode for H-2 evolution and CO2 reduction, but its efficiency is still far below the theoretical limit. To address this, a clear understanding of CuO's electronic structure is necessary, but there is no consensus on the orbital character of the photoexcited electron. This study uses femtosecond XANES spectra to track the element-specific dynamics of electrons and holes in CuO, and reveals the charge transfer state and mixing of conduction band states, providing valuable insight for theoretical modeling of electronic structures.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Multidisciplinary Sciences
Sergey D. Prosnyak, Daniel E. Maison, Leonid V. Skripnikov
Summary: Recently, the upper bounds on the T and P-violating eEDM and scalar-pseudoscalar nucleus-electron interaction in HfF+ cations have been updated. Two other sources of T and P-violation, ALP-mediated electron-electron and nucleus-electron interactions, were considered. A new method using ab initio relativistic coupled cluster theory was developed to estimate the effects of these interactions in HfF+.
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, Multidisciplinary
Samantha Carter, Wenjie Tao, Rajat Majumder, Alexander Yu. Sokolov, Shiyu Zhang
Summary: We investigate the spin switching behavior of dicopperoxo nitrosyl [Cu-2(O)(NO)](2+) complexes at different temperatures and its influence on hydrogen atom transfer (HAT) reactivity. Our findings indicate that the HAT reaction is predominantly mediated by the S = 1/2 isomer of [Cu-2(O)(NO)](2+) complexes at low temperatures (198 K). Moreover, the introduction of functional groups that create an unsymmetric secondary coordination environment enhances the HAT rates by perturbing the spin equilibria. These findings suggest that metalloenzymes in natural proteins may employ similar strategies to control HAT reactions due to their often unsymmetric coordination environments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Physics, Multidisciplinary
John W. Blanchard, Dmitry Budker, David DeMille, Mikhail G. Kozlov, Leonid V. Skripnikov
Summary: CeNTREX is developing an experiment using a TlF molecular beam to search for hadronic interactions that violate both time-reversal (T) and parity (P) invariance. They also propose to use the same beam to look for a T-invariance conserving but P-nonconserving (PNC) effect induced by the anapole moment of the Tl nucleus. To measure the nuclear anapole moment, they replace the dc electric and magnetic fields in CeNTREX with rf fields resonant with a nuclear spin-flip transition. They use the relativistic coupled-cluster method in combination with relativistic density functional theory to calculate the molecular PNC spin-spin vector coupling constant that links the experimental signal with the anapole moment. The calculated value of the P-conserving spin-spin coupling constant is in good agreement with available experimental data.
PHYSICAL REVIEW RESEARCH
(2023)
Article
Optics
Daniel E. Maison, Leonid V. Skripnikov, Gleb Penyazkov, Matt Grau, Alexander N. Petrov
Summary: The LuOH+ cation is a promising system to investigate the effects of time reversal and spatial parity violation. This study focuses on the manifestations of these effects induced by electron electric dipole moment (eEDM) and the scalar-pseudoscalar interaction of the nucleus with electrons (characterized by ks constant) in LuOH+. The calculations include the determination of enhancement factors, polarization in external electric fields, hyperfine interactions, and rovibrational structures. The findings are crucial for experimental preparations and the extraction of eEDM and ks values from experimental data.
Article
Optics
S. D. Chekhovskoi, D. V. Chubukov, L. V. Skripnikov, A. N. Petrov, L. N. Labzowsky
Summary: This paper discusses the mechanisms of the P, T-odd Faraday effect (PTFE), analyzing the possible existence of an atomic-level-mixing mechanism in addition to the linear Stark splitting mechanism. The analysis shows that with heavy diatomic molecules, particularly PbF, the contribution of the atomic-level-mixing mechanism may exceed that of the linear Stark splitting mechanism, making PbF a promising candidate for experiments studying P, T-odd effects.
Correction
Chemistry, Physical
Carlos E. V. de Moura, Alexander Yu. Sokolov
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
