TY - JOUR
T1 - Nonadiabatic Dynamics of Charge-Transfer States Using the Anthracene-Tetracyanoethylene Complex as a Prototype
AU - Siddique, Farhan
AU - Barbatti, Mario
AU - Cui, Zhonghua
AU - Lischka, Hans
AU - Aquino, Adelia J.A.
N1 - Funding Information:
We are grateful for the support from the School of Pharmaceutical Science and Technology (SPST), Tianjin University, Tianjin, China, including computer time on the SPST computer cluster Arran. Z.C. acknowledges the financial support from the Beijing National Laboratory for Molecular Sciences (BNLMS201910). M.B. thanks the support from the projects ANR PRC WSPLIT (ANR-17-CE05-0005-01) and Equip@Meso (ANR-10-EQPX-29-01).
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/4/30
Y1 - 2020/4/30
N2 - Surface hopping quantum mechanical/molecular dynamics simulations have been performed for the tetracyanoethylene-anthracene complex to investigate the evolution of charge-transfer (CT) states after excitation into a locally excited (LE) state of anthracene. The scaled opposite-spin (SOS) second-order algebraic diagrammatic construction (SOS-ADC(2)) has been used to achieve a balanced description of LE and CT states. The calculations have been performed for two media, the gas phase and water (described by molecular mechanics, MM). The two dynamics variants show strongly different behaviors. Even though in both cases the conversion from the LE state to lower-lying CT states occurs with 100 fs, in the gas phase, the system remains in the excited state for longer than 2 ps, while in water, it returns to the ground state within 0.5 ps. Moreover, while in the gas phase the original neutral equilibrium structure should be recovered, in water, the ion-pair (IPr) CT state is strongly stabilized, creating a new competing ground-state isomer. Thus, we predict that the ground state of the complex in water should be composed of two species, the original neutral state and an IPr state. The existence of an IPr ground state in strongly polar environments opens interesting possibilities for the design of efficient charge-separating organic donor-acceptor interfaces.
AB - Surface hopping quantum mechanical/molecular dynamics simulations have been performed for the tetracyanoethylene-anthracene complex to investigate the evolution of charge-transfer (CT) states after excitation into a locally excited (LE) state of anthracene. The scaled opposite-spin (SOS) second-order algebraic diagrammatic construction (SOS-ADC(2)) has been used to achieve a balanced description of LE and CT states. The calculations have been performed for two media, the gas phase and water (described by molecular mechanics, MM). The two dynamics variants show strongly different behaviors. Even though in both cases the conversion from the LE state to lower-lying CT states occurs with 100 fs, in the gas phase, the system remains in the excited state for longer than 2 ps, while in water, it returns to the ground state within 0.5 ps. Moreover, while in the gas phase the original neutral equilibrium structure should be recovered, in water, the ion-pair (IPr) CT state is strongly stabilized, creating a new competing ground-state isomer. Thus, we predict that the ground state of the complex in water should be composed of two species, the original neutral state and an IPr state. The existence of an IPr ground state in strongly polar environments opens interesting possibilities for the design of efficient charge-separating organic donor-acceptor interfaces.
UR - http://www.scopus.com/inward/record.url?scp=85084175258&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.0c01900
DO - 10.1021/acs.jpca.0c01900
M3 - Article
C2 - 32243162
AN - SCOPUS:85084175258
VL - 124
SP - 3347
EP - 3357
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 17
ER -