Molecular Calculations and Complexes. Self-Consistent Molecular Orbital Approach to the First and Second Charge-Transfer Transitions of Tetracyanoethylene-Aromatic Hydrocarbon Interactions

1967 ◽  
Vol 89 (22) ◽  
pp. 5523-5527 ◽  
Author(s):  
Arthur R. Lepley ◽  
Clifton C. Thompson, Jr.
Keyword(s):  
Charge Transfer ◽  
Aromatic Hydrocarbon ◽  
Molecular Orbital ◽  
Self Consistent ◽  
Charge Transfer Transitions ◽  
Molecular Calculations

Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon–tetracyanoethylene complexes

2014 ◽  
Vol 16 (38) ◽  
pp. 20586-20597 ◽  
Author(s):  
Adélia A. J. Aquino ◽  
Itamar Borges ◽  
Reed Nieman ◽  
Andreas Köhn ◽  
Hans Lischka
Keyword(s):  
Charge Transfer ◽  
Aromatic Hydrocarbon ◽  
Intermolecular Interactions ◽  
Electron Acceptor ◽  
Charge Transfer Transitions

ADC(2) calculations accurately describe charge transfer transitions in complexes of the tetracyanoethylene electron acceptor and three distinct aromatic donors.

Chemical Behavior of Charge-transfer Complexes, VI. Catalysis of Acetolysis of 2,4,7-Trinitro-9-fluorenyl p-Toluenesulfonate by Aromatic Hydrocarbon Donors

1974 ◽  
Vol 52 (22) ◽  
pp. 3748-3757 ◽  
Author(s):  
Allan K. Colter ◽  
Arthur L. McKenna ◽  
M. A. Kasem
Keyword(s):  
Charge Transfer ◽  
Aromatic Hydrocarbon ◽  
Transition State ◽  
Molecular Orbital ◽  
Orbital Energy ◽  
Charge Transfer Complexes ◽  
Substrate Complex ◽  
Donor Substrate ◽  
Highest Occupied Molecular Orbital ◽  
Π Complex

The catalytic effectiveness of eleven aromatic hydrocarbon donors in the acetolysis of 2,4,7-trinitro-9-fluorenyl p-toluenesulfonate (TNF-OTs) has been examined. For nine of these donors, the kinetic data were analyzed to obtain the rate constant, kc, for acetolysis of the 1:1 donor–substrate complex, and the 1:1 donor–substrate association constant, K. Two measures of catalytic effectiveness, log kc and log kcK correlate well with the highest occupied molecular orbital energy of the donor, E(HOMO), calculated by the Hückel molecular orbital (HMO) method. The success of these correlations is considered to mean that the transition state for acetolysis resembles a π-complex. A model based on Mulliken's charge-transfer theory in its simplest form leads to an estimate of 0.11 of an electron transferred from the donor to the acceptor substrate in the complexed transition state.

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>

Sign in / Sign up

Export Citation Format

Share Document