scholarly journals A non-perturbative pairwise-additive analysis of charge transfer contributions to intermolecular interaction energies

2021 ◽  
Author(s):  
Srimukh Prasad Veccham ◽  
Joonho Lee ◽  
Yuezhi Mao ◽  
Paul R. Horn ◽  
Martin Head-Gordon
Keyword(s):  
Charge Transfer ◽  
Intermolecular Interaction ◽  
Interaction Energies ◽  
Complete Decomposition ◽  
Charge Transfer Interaction

A non-perturbative scheme for complete decomposition of energy and charge associated with charge transfer interaction into pairwise additive components.

On the Nature of Halide-Water Interactions: Insights from Many-Body Representations and Density Functional Theory

2019 ◽  
Author(s):  
Brandon B. Bizzarro ◽  
Colin K. Egan ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Molecular Orbital ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Orbital Energy ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory

<div> <div> <div> <p>Interaction energies of halide-water dimers, X<sup>-</sup>(H<sub>2</sub>O), and trimers, X<sup>-</sup>(H<sub>2</sub>O)<sub>2</sub>, with X = F, Cl, Br, and I, are investigated using various many-body models and exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. Analysis of the results obtained with the many-body models demonstrates the need to capture important short-range interactions in the regime of large inter-molecular orbital overlap, such as charge transfer and charge penetration. Failure to reproduce these effects can lead to large deviations relative to reference data calculated at the coupled cluster level of theory. Decompositions of interaction energies carried out with the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method demonstrate that permanent and inductive electrostatic energies are accurately reproduced by all classes of XC functionals (from generalized gradient corrected (GGA) to hybrid and range-separated functionals), while significant variance is found for charge transfer energies predicted by different XC functionals. Since GGA and hybrid XC functionals predict the most and least attractive charge transfer energies, respectively, the large variance is likely due to the delocalization error. In this scenario, the hybrid XC functionals are then expected to provide the most accurate charge transfer energies. The sum of Pauli repulsion and dispersion energies are the most varied among the XC functionals, but it is found that a correspondence between the interaction energy and the ALMO EDA total frozen energy may be used to determine accurate estimates for these contributions. </p> </div> </div> </div>

Fluorescence Quenching of Aminodiphenylamines with Chloromethanes

2002 ◽  
Vol 67 (8) ◽  
pp. 1154-1164 ◽  
Author(s):  
Nachiappan Radha ◽  
Meenakshisundaram Swaminathan
Keyword(s):  
Charge Transfer ◽  
Fluorescence Quenching ◽  
Ground State ◽  
Rate Constants ◽  
Quenching Mechanism ◽  
Quenching Rate ◽  
Charge Transfer Interaction ◽  
Electronically Excited ◽  
A Charge

The fluorescence quenching of 2-aminodiphenylamine (2ADPA), 4-aminodiphenylamine (4ADPA) and 4,4'-diaminodiphenylamine (DADPA) with tetrachloromethane, chloroform and dichloromethane have been studied in hexane, dioxane, acetonitrile and methanol as solvents. The quenching rate constants for the process have also been obtained by measuring the lifetimes of the fluorophores. The quenching was found to be dynamic in all cases. For 2ADPA and 4ADPA, the quenching rate constants of CCl4 and CHCl3 depend on the viscosity, whereas in the case of CH2Cl2, kq depends on polarity. The quenching rate constants for DADPA with CCl4 are viscosity-dependent but the quenching with CHCl3 and CH2Cl2 depends on the polarity of the solvents. From the results, the quenching mechanism is explained by the formation of a non-emissive complex involving a charge-transfer interaction between the electronically excited fluorophores and ground-state chloromethanes.

Enantioselective Nucleophilic Aromatic Substitution Reaction of Azlactones to Synthesize Quaternary α-Amino Acid Derivatives

Synlett ◽  
2020 ◽  
Author(s):  
Xiaohua Liu ◽  
Yi Li ◽  
Hao Pan ◽  
Wang-Yuren Li ◽  
Xiaoming Feng
Keyword(s):  
Hydrogen Bonding ◽  
Charge Transfer ◽  
Amino Acid ◽  
Substitution Reaction ◽  
Nucleophilic Aromatic Substitution ◽  
Amino Acid Derivatives ◽  
Amino Acid Esters ◽  
Aromatic Substitution ◽  
Charge Transfer Interaction ◽  
Acid Esters

AbstractAn asymmetric organocatalytic nucleophilic aromatic substitution reaction of azlactones with electron-deficient aryls was established. A variety of α-aryl α-alkyl α-amino acid esters and peptides were obtained in decent yields and stereoselectivities. A new bifunctional catalytic mode involving charge-transfer interaction and hydrogen bonding is proposed to explain the enantioselectivity.

scholarly journals Color-tunable arylaminoanthraquinone dyes through hydrogen-bond-assisted charge transfer interaction

RSC Advances ◽  
2021 ◽  
Vol 11 (39) ◽  
pp. 24217-24231
Author(s):  
Takashi Takeda ◽  
Yotaro Kasahara ◽  
Tomoyuki Akutagawa
Keyword(s):  
Hydrogen Bond ◽  
Charge Transfer ◽  
Charge Transfer Interaction ◽  
Color Tunable

A color-tunable anthraquinone library based on arylaminoanthraquinone was prepared through hydrogen-bond-assisted charge transfer interaction.

scholarly journals Intermolecular interaction energies in transition metal coordination compounds

CrystEngComm ◽  
2015 ◽  
Vol 17 (48) ◽  
pp. 9300-9310 ◽  
Author(s):  
Andrew G. P. Maloney ◽  
Peter A. Wood ◽  
Simon Parsons
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Crystal Structures ◽  
Intermolecular Interaction ◽  
Coordination Compounds ◽  
Metal Coordination ◽  
Interaction Energies

The PIXEL method has been parameterised and validated for transition metals, extending its applicability from ~40% to ~85% of all published crystal structures.

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