Multifaceted ultrafast intramolecular charge transfer dynamics of 4-(dimethylamino)benzonitrile (DMABN)

Myeongkee Park; Chul Hoon Kim; Taiha Joo

doi:10.1021/jp310842z

Multifaceted ultrafast intramolecular charge transfer dynamics of 4-(dimethylamino)benzonitrile (DMABN)

Myeongkee Park
, Chul Hoon Kim
, Taiha Joo^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

58 Citations (Scopus)

Abstract

Intramolecular charge transfer (ICT) of DMABN has been the subject of extensive investigations. Through the measurements of highly time-resolved fluorescence spectra (TRFS) over the whole emission region, we have examined the ICT dynamics of DMABN in acetonitrile free from the solvation dynamics and vibronic relaxation. The ICT dynamics was found to be characterized by a broad range of time scales; nearly instantaneous (<30 fs), 160 fs, and 3.3 ps. TRFS revealed that an ICT state with partially twisted geometry, ICT(P), is formed within a few hundred femtoseconds either directly from the initial photoexcited state or via the locally excited (LE) state. The ICT(P) state undergoes further relaxation along the intramolecular nuclear coordinate to reach the twisted ICT (TICT) state with the time constant of 4.8 ps. A conformational diversity along the rotation of the dimethylamino group was speculated to account for the observed diffusive dynamics.

Original language	English
Pages (from-to)	370-377
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	117
Issue number	2
DOIs	https://doi.org/10.1021/jp310842z
Publication status	Published - 2013 Jan 17
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1021/jp310842z

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title = "Multifaceted ultrafast intramolecular charge transfer dynamics of 4-(dimethylamino)benzonitrile (DMABN)",

abstract = "Intramolecular charge transfer (ICT) of DMABN has been the subject of extensive investigations. Through the measurements of highly time-resolved fluorescence spectra (TRFS) over the whole emission region, we have examined the ICT dynamics of DMABN in acetonitrile free from the solvation dynamics and vibronic relaxation. The ICT dynamics was found to be characterized by a broad range of time scales; nearly instantaneous (<30 fs), 160 fs, and 3.3 ps. TRFS revealed that an ICT state with partially twisted geometry, ICT(P), is formed within a few hundred femtoseconds either directly from the initial photoexcited state or via the locally excited (LE) state. The ICT(P) state undergoes further relaxation along the intramolecular nuclear coordinate to reach the twisted ICT (TICT) state with the time constant of 4.8 ps. A conformational diversity along the rotation of the dimethylamino group was speculated to account for the observed diffusive dynamics.",

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T1 - Multifaceted ultrafast intramolecular charge transfer dynamics of 4-(dimethylamino)benzonitrile (DMABN)

AU - Park, Myeongkee

AU - Kim, Chul Hoon

AU - Joo, Taiha

PY - 2013/1/17

Y1 - 2013/1/17

N2 - Intramolecular charge transfer (ICT) of DMABN has been the subject of extensive investigations. Through the measurements of highly time-resolved fluorescence spectra (TRFS) over the whole emission region, we have examined the ICT dynamics of DMABN in acetonitrile free from the solvation dynamics and vibronic relaxation. The ICT dynamics was found to be characterized by a broad range of time scales; nearly instantaneous (<30 fs), 160 fs, and 3.3 ps. TRFS revealed that an ICT state with partially twisted geometry, ICT(P), is formed within a few hundred femtoseconds either directly from the initial photoexcited state or via the locally excited (LE) state. The ICT(P) state undergoes further relaxation along the intramolecular nuclear coordinate to reach the twisted ICT (TICT) state with the time constant of 4.8 ps. A conformational diversity along the rotation of the dimethylamino group was speculated to account for the observed diffusive dynamics.

AB - Intramolecular charge transfer (ICT) of DMABN has been the subject of extensive investigations. Through the measurements of highly time-resolved fluorescence spectra (TRFS) over the whole emission region, we have examined the ICT dynamics of DMABN in acetonitrile free from the solvation dynamics and vibronic relaxation. The ICT dynamics was found to be characterized by a broad range of time scales; nearly instantaneous (<30 fs), 160 fs, and 3.3 ps. TRFS revealed that an ICT state with partially twisted geometry, ICT(P), is formed within a few hundred femtoseconds either directly from the initial photoexcited state or via the locally excited (LE) state. The ICT(P) state undergoes further relaxation along the intramolecular nuclear coordinate to reach the twisted ICT (TICT) state with the time constant of 4.8 ps. A conformational diversity along the rotation of the dimethylamino group was speculated to account for the observed diffusive dynamics.

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SN - 1089-5639

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JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

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ER -

Multifaceted ultrafast intramolecular charge transfer dynamics of 4-(dimethylamino)benzonitrile (DMABN)

Abstract

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