title: Theoretical studies of the ground and excited state structures of stilbene.
abstract: Optimized geometries are evaluated for the ground and low lying excited states of cis-stilbene, trans-stilbene, and 4a,4b-dihydrophenanthrene (DHP) from calculations performed with the improved virtual orbital, complete active space configuration interaction (IVO-CASCI) method. The calculations indicate that a nonplanar conformer of trans-stilbene is the most stable among the isomers. The calculated ground and low lying excited state geometries agree well with experiment and with prior theoretical estimates where available. Our IVO-CASCI based multireference Möller-Plesset (MRMP) computations place the (1)B(u) state of trans stilbene to be ∼4.0 eV above the ground X(1)A(g) state, which is in accord with experiment and with earlier theoretical estimates. The 1(1)B(u) state of trans-stilbene can be represented by the highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) transition (ionic type) from the ground state, whereas its 2(1)B(u) state is dominated by the HOMO → LUMO+1 and HOMO-1 → LUMO transitions (covalent type). Likewise, the 1(1)B and 2(1)B states of cis-stilbene and DHP are also found to be of ionic and covalent types, respectively.
authors.affiliation: Indian Institute of Astrophysics , Bangalore 560034, India.
authors.forename: Rajat K
authors.initials: RK
authors.lastname: Chaudhuri
authors.forename: Karl F
authors.initials: KF
authors.lastname: Freed
authors.forename: Sudip
authors.initials: S
authors.lastname: Chattopadhyay
authors.forename: Uttam Sinha
authors.initials: US
authors.lastname: Mahapatra