Molecules under external electric field: On the changes in the electronic structure and validity limits of the theoretical predictions

Abstract

A detailed analysis of the electronic structure of the ground and first excited spin state of three diatomic molecules ( N2, BH and CO) under static applied electric field is performed at CCSD(T), DFT, MRCI and MRCI(Q) levels of theory. Our findings have revealed that by boosting the applied field one induces changes in the occupation numbers of molecular orbitals, giving rise to changes in the equilibrium geometry and in the HOMO-LUMO energy gap. Specifically, singlet to triplet spin transition can be induced by increasing the applied electric field beyond a critical value. Accordingly, affecting the accuracy of the widely used expression of energy expanded in Taylor series with respect to the applied electric field. © 2018 Wiley Periodicals, Inc.

Twistable dipolar aryl rings as electric field actuated conformational molecular switches

“…Such E-field-induced stabilization of Rydberg orbitals is in line with the results recently found for ethylene in intense laser fields 54. In broader terms, the strong decrease of the HOMO-LUMO gap found for biphenyl derivatives under large fields is also in line with the results reported in Ref 55. for diatomic molecules, where a large decrease in the gap was observed for E-fields larger than 5 x 10 7 V/cm.…”

Model of B9N9 Response under External Electric Field: Geometry, Electronic Properties, Reaction Activity

“…External electric fields (EEF) usually change the internal and external electronic environments of molecules [ 18 , 19 ] and disrupt their geometric structure [ 20 , 21 , 22 , 23 ]. It is expected that EEF will have a strong influence on B 9 N 9 geometry, electrons, and reactivity properties.…”

Hubbard pair cluster in the external fields. Studies of the polarization and susceptibility

“…Some examples can be recalled here, mainly to mention the molecular dimer systems. Among them molecular mixed-valence dimers [89][90][91][92][93][94] or κ-(BEDT-TTF) [95] focus particular attention and appear highly promising; however, also some non-molecular systems such as dimers on graphene surface [96] also attract the interest.…”