Reappraisal of cis effect in 1,2-dihaloethenes: An improved virtual orbital multireference approach

Chaudhuri, Rajat K.; Hammond, Jeff R.; Freed, Karl F.; Chattopadhyay, Sudip; Mahapatra, Uttam Sinha

doi:doi:10.1063/1.2958284

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Phase-separation transition in liquid mixtures near curved charged objects

We study the thermodynamic behavior of nonpolar liquid mixtures in the vicinity of curved charged objects, such as electrodes or charged colloids. There is a critical value of charge (or potential), above which a phase-separation transition occurs, and the interface between high- and low-dielectric constant components becomes sharp. Analytical and numerical composition profiles are given, and the equilibrium front location as a function of charge or voltage is found. We further employ a simple C...

A gradient-directed Monte Carlo approach to molecular design

The recently developed linear combination of atomic potentials (LCAP) approach [ M. Wang et al., J. Am. Chem. Soc. 128, 3228 (2006) ] allows continuous optimization in a discrete chemical space, and thus is useful in the design of molecules for targeted properties. To address further challenges arising from the rugged, continuous property surfaces in the LCAP approach, we develop a gradient-directed Monte Carlo (GDMC) strategy as an augmentation to the original LCAP optimization method. The GDM...

Computed relative stabilities for isomers of 1,2-difluoroethene and 1,2-dichloroethene isomers are compared with predictions based on chemical hardness (η) and electrophilicity (ω) using the principles of maximum hardness and minimum electrophilicity. The chemical hardness and electrophilicity deduced either from improved virtual orbital (IVO) energies or from correlated treatments correctly predict that cis 1,2-difluoroethene and 1,2-dichloroethene are energetically more stable than the corresponding trans isomers, and the ground state energies from multireference perturbation theory with IVO orbitals agree with these predictions. However, when the same quantities are computed using Hartree–Fock orbitals, serious inconsistencies between the two approaches emerge in predicting the stability of the isomers of the 1,2-dihaloethenes. The present study clearly demonstrates that the IVO energies are appropriate for the computation of hardness related parameters, notably the chemical hardness and electrophilicity. Moreover, the IVO methods also provide smooth potential energy curves for the cis-trans isomerization of the two 1,2-dihaloethenes.

Article Outline

INTRODUCTION
GENERATION OF IMPROVED VIRTUAL ORBITALS
THEORETICAL BACKGROUND FOR IVO-MRPT METHOD
RESULTS AND DISCUSSION
1. Structures and relative energies of cis - and trans 1,2-difluoroethenes
2. Stability and chemical hardness
3. Torsional PEC for 1,2-difluoroethene
CONCLUDING REMARKS

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KEYWORDS and PACS

Keywords

HF calculations, isomerisation, organic compounds, perturbation theory, potential energy surfaces

PACS

82.30.Qt

Isomerization and rearrangement
82.20.Kh

Potential energy surfaces for chemical reactions

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http://link.aip.org/link/doi/10.1063/1.2958284

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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