The antisymmetrized geminal power (AGP) wave function has a long history and is known by different names in various chemical and physical problems. There has been recent interest in using AGP as a starting point for strongly correlated electrons. Here, we show that in a seniority-conserving regime, different AGP-based correlator representations based on generators of the algebra, killing operators, and geminal replacement operators are all equivalent. We implement one representation that uses number operators as correlators and has linearly independent curvilinear metrics to distinguish the regions of Hilbert space. This correlation method called -CI provides excellent accuracy in energies when applied to the pairing Hamiltonian.
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http://dx.doi.org/10.1021/acs.jctc.0c00807 | DOI Listing |
J Phys Chem A
April 2023
National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba 305-8506, Japan.
Levoglucosan (Levo) is a major saccharide formed by the combustion of cellulosic materials. Levo was once considered an inert tracer of biomass-burning aerosols; however, recent studies have indicated that Levo in atmospheric condensed phases does indeed react with atmospheric reactants. Here, we report the results of a time-resolved mass spectrometric study of the oxidation of Levo in aqueous solutions with ferrous ion (Fe)/hydrogen peroxide (HO) (i.
View Article and Find Full Text PDFInorg Chem
October 2021
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.
A set of Pd(II) biladiene complexes bearing different combinations of methyl- and phenyl-substituents on the sp-hybridized -carbon (the 10-position of the biladiene framework) was prepared and studied. In addition to a previously described Pd(II) biladiene complex bearing geminal dimethyl substituents a the 10-position (), homologous Pd(II) biladienes bearing geminal methyl and phenyl substituents () and geminal diphenyl groups() were prepared and structurally characterized. Detailed electrochemical as well as steady-state and time-resolved spectroscopic experiments were undertaken to evaluate the influence of the substituents on the biladiene's tetrahedral -carbon.
View Article and Find Full Text PDFInorg Chem
October 2021
Theoretical Sciences Unit, School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India.
Tetrel Lewis acids are a prospective alternative to commonly employed neutral boranes in frustrated Lewis pair (FLP) chemistry. While cationic tetrylium Lewis acids, being isolobal and iso(valence)electronic, are a natural replacement to boranes, neutral tetrel Lewis acids allude as less trivial options due to the absence of a formally empty p orbital on the acceptor atom. Recently, a series of intramolecular geminal FLPs (E = Si, Ge, Sn) featuring neutral tetrel atoms as acceptor sites has been reported for activation of small molecules including H.
View Article and Find Full Text PDFDalton Trans
June 2021
Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.
Diversity-oriented synthesis of energetic pyrimidine structures with geminal explosophoric groups of geminal dinitro and azido-nitro groups via a novel reductive cleavage and oxidative coupling strategy is reported. Fluorine has also been introduced for the first time based on the nucleophilic coupling process. The obtained energetic pyrimidines are investigated via X-ray diffraction and theoretical techniques of electrostatic potential and proton affinity calculations.
View Article and Find Full Text PDFJ Mol Model
May 2021
Department of Physics, Bharathiar University, Coimbatore, Tamil Nadu, 641046, India.
In this work, we have theoretically studied the dicationic ionic liquids (DILs) constructed from geminal methylimidazolium dication with varying amino acid anions and spacers using density functional theory. Amino acid-based DILs form via strong C-H···O hydrogen bonds. These hydrogen bonds have a significant role in stabilizing the DILs.
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