Photorelaxation Pathways of 4-(N,N-Dimethylamino)-4'-nitrostilbene Upon S1 Excitation Revealed by Conical Intersection and Intersystem Crossing Networks.
Molecules
; 25(9)2020 May 09.
Article
in En
| MEDLINE
| ID: mdl-32397393
ABSTRACT
Multi-state n-electron valence state second order perturbation theory (MS-NEVPT2) was utilized to reveal the photorelaxation pathways of 4-(N,N-dimethylamino)-4'-nitrostilbene (DANS) upon S1 excitation. Within the interwoven networks of five S1/S0 and three T2/T1 conical intersections (CIs), and three S1/T2, one S1/T1 and one S0/T1 intersystem crossings (ISCs), those competing nonadiabatic decay pathways play different roles in trans-to-cis and cis-to-trans processes, respectively. After being excited to the Franck-Condon (FC) region of the S1 state, trans-S1-FC firstly encounters an ultrafast conversion to quinoid form. Subsequently, the relaxation mainly proceeds along the triplet pathway, trans-S1-FC â ISC-S1/T2-trans â CI-T2/T1-trans â ISC-S0/T1-twist â trans- or cis-S0. The singlet relaxation pathway mediated by CI-S1/S0-twist-c is hindered by the prominent energy barrier on S1 surface and by the reason that CI-S1/S0-trans and CI-S1/S0-twist-t are both not energetically accessible upon S1 excitation. On the other hand, the cis-S1-FC lies at the top of steeply decreasing potential energy surfaces (PESs) towards the CI-S1/S0-twist-c and CI-S1/S0-DHP regions; therefore, the initial twisting directions of DN and DAP moieties determine the branching ratio between αC=C twisting (cis-S1-FC â CI-S1/S0-twist-c â trans- or cis-S0) and DHP formation relaxation pathways (cis-S1-FC â CI-S1/S0-DHP â DHP-S0) on the S1 surface. Moreover, the DHP formation could also take place via the triplet relaxation pathway, cis-S1-FC â ISC-S1/T1-cis â DHP-T1 â DHP-S0, however, which may be hindered by insufficient spin-orbit coupling (SOC) strength. The other triplet pathways for cis-S1-FC mediated by ISC-S1/T2-cis are negligible due to the energy or geometry incompatibility of possible consecutive stepwise S1 â T2 â T1 or S1 â T2 â S1 processes. The present study reveals photoisomerization dynamic pathways via conical intersection and intersystem crossing networks and provides nice physical insight into experimental investigation of DANS.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Stilbenes
Language:
En
Journal:
Molecules
Journal subject:
BIOLOGIA
Year:
2020
Document type:
Article
Affiliation country:
China