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Effect of Broken Symmetry on the First Hyperpolarizability of a Centrosymmetric Molecule with an Application to Furan‐Containing [2.2]Cyclophandiene
Author(s) -
Chang YaoWen,
Jin BihYaw
Publication year - 2010
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201000081
Subject(s) - hyperpolarizability , chemistry , molecule , bistability , molecular physics , symmetry (geometry) , computational chemistry , quantum , chemical physics , quantum mechanics , physics , polarizability , geometry , organic chemistry , mathematics
The effects of broken symmetry on the first hyperpolarizability for centrosymmetric molecules are studied with the so‐called VB‐4CT model. We show that the first hyperpolarizability can be enhanced dramatically when certain centrosymmetric molecules with intrinsic bistable adiabatic potential surface has its symmetry broken due to the external asymmetric perturbation, albeit this value should vanish when no any asymmetric external field is present. Particularly, we discover that the stiffness of molecular geometry and the susceptibility to weak asymmetric perturbation are related to the extent of charge‐transfer exciton in its electronic ground state. This mechanism is then successfully applied to the exceptionally high first hyperpolarizability of furan‐containing [2.2]cyclophandiene with inversion symmetry by combining the simple VB‐4CT model and quantum chemical calculation.