Theoretical study of solvent effect on one- and two-photon absorption properties of starburst DCM derivatives.
The equilibrium geometries, electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of starburst 4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) derivatives have been studied by using density functional theory (DFT) and Zerner's intermediate neglect of differential overlap (ZINDO) program. Results showed that increasing the number of branches in DCM molecules and introducing stronger electron withdrawing groups are efficient ways to enhance the TPA cross sections. For the two- and three-branched molecules of the DCM derivatives, the solvent effect on the OPA and TPA properties was also considered by adapting the self-consistent reaction field (SCRF) theory with the polarizable continuum model (PCM) to model the interaction with the solvent in ZINDO program. The calculated molecular structure, transition dipole moment and intramolecular charge transfer (ICT) in different solvents have been analyzed to approximate how the solvent affects the TPA cross section. Results indicated that the TPA cross section increases as the polarity of the solvents increases, and it reaches a maximum when the dielectric constant epsilon equals 20.7.
Zhao
Yang
Y
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, People's Republic of China.
Ren
Ai-Min
AM
Feng
Ji-Kang
JK
Zhou
Xin
X
Ai
Xi-Cheng
XC
Su
Wen-Jie
WJ
D004396:Coloring Agents / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D017785:Photons; D011714:Pyrans / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013343:Styrenes / Q000737:chemistry*
D004396:Coloring Agents; D011714:Pyrans; D012997:Solvents; D013343:Styrenes; C082825:4-(dicyanomethylene)-2-methyl-6-(4-(dimethylamino)styryl)-4H-pyran