Yu-ling Chu, Zhong Yang, Zhe-feng Pan, Jing Liu, Yue-yi Han, Yong Ding, Peng Song. Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory[J]. Chinese Journal of Chemical Physics , 2012, 25(6): 654-658. doi: 10.1088/1674-0068/25/06/654-658
Citation: Yu-ling Chu, Zhong Yang, Zhe-feng Pan, Jing Liu, Yue-yi Han, Yong Ding, Peng Song. Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory[J]. Chinese Journal of Chemical Physics , 2012, 25(6): 654-658. doi: 10.1088/1674-0068/25/06/654-658

Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory

doi: 10.1088/1674-0068/25/06/654-658
Funds:  This work was supported by the Program of Shenyang Key Laboratory of Optoelectronic materi-als and technology (No.F12-254-1-00), the National Natural Science Foundation of China (No.11274149 and No.21271095), the Natural Science Founda-tion of Liaoning Province of China (No.20111035, No.201102080, and No.20121032), Liaoning Provincial Department of Education Project (No.L20111003), and the Natural Science Foundation of Liaoning University (No.2011LDGY10). The results of quantum chemical calculations described in this work were obtained on the homemade Linux cluster of group 1101, Dalian Institute of Chemical Physics.
  • Received Date: 2012-08-20
  • Density functional theory and time-dependent density-functional theory have been used to investigate the photophysical properties and relaxation dynamics of dimethylaminobenzophe-none (DMABP) and its hydrogen-bonded DMABP-MeOH dimer. It is found that, in non-polar aprotic solvent, the transitions from S0 to S1 and S2 states of DMABP have both n→π* and π→π* characters, with the locally excited feature mainly located on the C=O group and the partial CT one characterized by electron transfer mainly from the dimethylaminophenyl group to the C=O group. But when the intermolecular hydrogen bond C=O…H-O is formed, the highly polar intramolecular charge transfer character switches over to the first excited state of DMABP-MeOH dimer and the energy difference between the two low-lying electronically excited states increases. To gain insight into the relaxation dynamics of DMABP and DMABP-MeOH dimer in the excited state, the potential energy curves for con-formational relaxation are calculated. The formation of twisted intramolecular charge trans-fer state via diffusive twisting motion of the dimethylamino/dimethylaminophenyl groups is found to be the major relaxation process. In addition, the decay of the S1 state of DMABP-MeOH dimer to the ground state, through nonradiative intermolecular hydrogen bond stretching vibrations, is facilitated by the formation of the hydrogen bond between DMABP and alcohols.
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Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory

doi: 10.1088/1674-0068/25/06/654-658
Funds:  This work was supported by the Program of Shenyang Key Laboratory of Optoelectronic materi-als and technology (No.F12-254-1-00), the National Natural Science Foundation of China (No.11274149 and No.21271095), the Natural Science Founda-tion of Liaoning Province of China (No.20111035, No.201102080, and No.20121032), Liaoning Provincial Department of Education Project (No.L20111003), and the Natural Science Foundation of Liaoning University (No.2011LDGY10). The results of quantum chemical calculations described in this work were obtained on the homemade Linux cluster of group 1101, Dalian Institute of Chemical Physics.

Abstract: Density functional theory and time-dependent density-functional theory have been used to investigate the photophysical properties and relaxation dynamics of dimethylaminobenzophe-none (DMABP) and its hydrogen-bonded DMABP-MeOH dimer. It is found that, in non-polar aprotic solvent, the transitions from S0 to S1 and S2 states of DMABP have both n→π* and π→π* characters, with the locally excited feature mainly located on the C=O group and the partial CT one characterized by electron transfer mainly from the dimethylaminophenyl group to the C=O group. But when the intermolecular hydrogen bond C=O…H-O is formed, the highly polar intramolecular charge transfer character switches over to the first excited state of DMABP-MeOH dimer and the energy difference between the two low-lying electronically excited states increases. To gain insight into the relaxation dynamics of DMABP and DMABP-MeOH dimer in the excited state, the potential energy curves for con-formational relaxation are calculated. The formation of twisted intramolecular charge trans-fer state via diffusive twisting motion of the dimethylamino/dimethylaminophenyl groups is found to be the major relaxation process. In addition, the decay of the S1 state of DMABP-MeOH dimer to the ground state, through nonradiative intermolecular hydrogen bond stretching vibrations, is facilitated by the formation of the hydrogen bond between DMABP and alcohols.

Yu-ling Chu, Zhong Yang, Zhe-feng Pan, Jing Liu, Yue-yi Han, Yong Ding, Peng Song. Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory[J]. Chinese Journal of Chemical Physics , 2012, 25(6): 654-658. doi: 10.1088/1674-0068/25/06/654-658
Citation: Yu-ling Chu, Zhong Yang, Zhe-feng Pan, Jing Liu, Yue-yi Han, Yong Ding, Peng Song. Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory[J]. Chinese Journal of Chemical Physics , 2012, 25(6): 654-658. doi: 10.1088/1674-0068/25/06/654-658

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