Electric Dipole Polarizability of Atoms by the Hartree—Fock Method. I. Theory for Closed‐Shell Systems

1965 ◽  
Vol 43 (10) ◽  
pp. S34-S39 ◽  
Author(s):  
Howard D. Cohen ◽  
C. C. J. Roothaan
Keyword(s):  
Electric Dipole ◽  
Closed Shell ◽  
Dipole Polarizability ◽  
Hartree Fock

Electric dipole and quadrupole moment and dipole polarizability of CS, SiO and SiS

2000 ◽  
Vol 98 (8) ◽  
pp. 481-491 ◽  
Author(s):  
George Maroulis, Constantinos Makris, Deme
Keyword(s):  
Quadrupole Moment ◽  
Electric Dipole ◽  
Dipole Polarizability

Full Optical Rotation Tensor at CCSD Level in the Modified Velocity Gauge

2020 ◽  
Author(s):  
Kaihua Zhang ◽  
Ty Balduf ◽  
Marco Caricato
Keyword(s):  
Electric Dipole ◽  
Optical Rotation ◽  
Electric Quadrupole ◽  
Polarizability Tensor ◽  
Dipole Polarizability ◽  
Difficult Case ◽  
Computationally Efficient ◽  
Rotation Tensor ◽  
Approximate Methods ◽  
Velocity Gauge

<div> <div> <p> </p><div> <div> <div> <p>This work presents the first simulations of the full optical rotation (OR) tensor at coupled cluster with single and double excitations (CCSD) level in the modified velocity gauge (MVG) formalism. The CCSD-MVG OR tensor is origin independent, and each tensor element can in principle be related directly to experimental measurements on oriented systems. We compare the CCSD results with those from two density functionals, B3LYP and CAM-B3LYP, on a test set of 22 chiral molecules. The results show that the functionals consistently overestimate the CCSD results for the individual tensor components and for the trace (which is related to the isotropic OR), by 10-20% with CAM-B3LYP and 20-30% with B3LYP. The data show that the contribution of the electric dipole-magnetic dipole polarizability tensor to the OR tensor is on average twice as large as that of the electric dipole-electric quadrupole polarizability tensor. The difficult case of (1S,4S)-(–)-norbornenone also reveals that the evaluation of the former polarizability tensor is more sensitive than the latter. We attribute the better agreement of CAM-B3LYP with CCSD to the ability of this functional to better reproduce electron delocalization compared with B3LYP, consistently with previous reports on isotropic OR. The CCSD-MVG approach allows the computation of reference data of the full OR tensor, which may be used to test more computationally efficient approximate methods that can be employed to study realistic models of optically active materials. </p> </div> </div> </div> </div> </div>

Polaronic and Bipolaronic Enhancement of Second Hyperpolarizabilities in Dithienyl Polyenes from Ab Initio Quantum Methods

1999 ◽  
Vol 597 ◽  
Author(s):  
Steven Trohalaki ◽  
Robert J. Zellmer ◽  
Ruth Pachter
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Valence Bond ◽  
Closed Shell ◽  
Functional Theory ◽  
Molecular Conformations ◽  
Hartree Fock ◽  
Molecular Charge ◽  
Field Methodology ◽  
Moller Plesset

AbstractSpangler and He [1,2] have shown that dithienyl polyenes form extremely stable bipolaronic dications when oxidatively doped in solution. Previous theoretical studies applied empirical methods to predict bipolaronic enhancement of hyperpolarizabilities for simple polyenes [3,4]. Here, we employ density functional theory to optimize the gas-phase molecular conformations of neutral, cationic, and dicationic forms of a series of dithienyl polyenes, where the number of ethene units, N, is varied from 1–5. Ab initio Hartree-Fock, generalized valence bond, configuration interaction, and Møller-Plesset calculations demonstrate that the dications are farily well described with a closed shell and therefore have little biradicaloid character. Second hyperpolarizabilities, γ, are subsequently calculated using ab initio Hartree-Fock theory and a finite field methodology. As expected, γ increases with the number of ethene units for a given molecular charge. The cations also show the largest increase in γ with N. For a given value of N, the cations display the largest γ values. However, if we treat the dication as a triplet, which might be present in solution, then it displays the largest γ.

scholarly journals Electric dipole polarizability from first principles calculations

2016 ◽  
Vol 94 (3) ◽  
Author(s):  
M. Miorelli ◽  
S. Bacca ◽  
N. Barnea ◽  
G. Hagen ◽  
G. R. Jansen ◽  
...  
Keyword(s):  
Electric Dipole ◽  
First Principles ◽  
Dipole Polarizability ◽  
First Principles Calculations

Calculation of optical characteristics of atoms with a closed shell by the Hartree-Fock-Roothaan method

2004 ◽  
Vol 96 (2) ◽  
pp. 192-194 ◽  
Author(s):  
M. N. Adamov ◽  
Yu. B. Malykhanov ◽  
V. V. Meshkov ◽  
R. M. Chadin
Keyword(s):  
Closed Shell ◽  
Optical Characteristics ◽  
Hartree Fock
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