Ultrafast Excited-State Dynamics of CuBr3- Complex Studied with Sub-20 fs Resolution

Taras A Khvorost; Leonid Yu Beliaev; Yuto Masaoka; Tsubasa Hidaka; Olesya S Myasnikova; Alexey S Ostras; Nikita A Bogachev; Mikhail Yu Skripkin; Maxim S Panov; Mikhail N Ryazantsev; Yutaka Nagasawa; Andrey S.  Mereshchenko

doi:10.1021/acs.jpcb.1c03797

Ultrafast Excited-State Dynamics of CuBr₃- Complex Studied with Sub-20 fs Resolution

Taras A Khvorost, Leonid Yu Beliaev, Yuto Masaoka, Tsubasa Hidaka, Olesya S Myasnikova, Alexey S Ostras, Nikita A Bogachev, Mikhail Yu Skripkin, Maxim S Panov, Mikhail N Ryazantsev, Yutaka Nagasawa, Andrey S. Mereshchenko^*

^*Corresponding author for this work

Research output: Contribution to journal › Journal article › Research › peer-review

Abstract

Ultrafast excited-state dynamics of CuBr₃- complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr₃- complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr₃- complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr3- complex exists as [CuBr₃(CH₃CN)₂]-, whereas three forms of this complex, [CuBr₃CH₂Cl₂]-, [CuBr₃(CH₂Cl₂)₂]-, and [CuBr₃(CH₂Cl₂)₃]-, are present in equilibrium in dichloromethane.

Original language	English
Journal	Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Volume	125
Issue number	26
Pages (from-to)	7213-7221
ISSN	1520-6106
DOIs	https://doi.org/10.1021/acs.jpcb.1c03797
Publication status	Published - 2021

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Khvorost, T. A., Beliaev, L. Y., Masaoka, Y., Hidaka, T., Myasnikova, O. S., Ostras, A. S., Bogachev, N. A., Skripkin, M. Y., Panov, M. S., Ryazantsev, M. N., Nagasawa, Y., & Mereshchenko, A. S. (2021). Ultrafast Excited-State Dynamics of CuBr₃- Complex Studied with Sub-20 fs Resolution. Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, 125(26), 7213-7221. https://doi.org/10.1021/acs.jpcb.1c03797

@article{6de5700726fc4826bf00ae5585cb3813,

title = "Ultrafast Excited-State Dynamics of CuBr3- Complex Studied with Sub-20 fs Resolution",

abstract = "Ultrafast excited-state dynamics of CuBr3- complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr3- complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr3- complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr3- complex exists as [CuBr3(CH3CN)2]-, whereas three forms of this complex, [CuBr3CH2Cl2]-, [CuBr3(CH2Cl2)2]-, and [CuBr3(CH2Cl2)3]-, are present in equilibrium in dichloromethane.",

author = "Khvorost, \{Taras A\} and Beliaev, \{Leonid Yu\} and Yuto Masaoka and Tsubasa Hidaka and Myasnikova, \{Olesya S\} and Ostras, \{Alexey S\} and Bogachev, \{Nikita A\} and Skripkin, \{Mikhail Yu\} and Panov, \{Maxim S\} and Ryazantsev, \{Mikhail N\} and Yutaka Nagasawa and Mereshchenko, \{Andrey S.\}",

year = "2021",

doi = "10.1021/acs.jpcb.1c03797",

language = "English",

volume = "125",

pages = "7213--7221",

journal = "Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces \& Biophysical",

issn = "1520-6106",

publisher = "American Chemical Society",

number = "26",

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Khvorost, TA, Beliaev, LY, Masaoka, Y, Hidaka, T, Myasnikova, OS, Ostras, AS, Bogachev, NA, Skripkin, MY, Panov, MS, Ryazantsev, MN, Nagasawa, Y & Mereshchenko, AS 2021, 'Ultrafast Excited-State Dynamics of CuBr₃- Complex Studied with Sub-20 fs Resolution', Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, vol. 125, no. 26, pp. 7213-7221. https://doi.org/10.1021/acs.jpcb.1c03797

Ultrafast Excited-State Dynamics of CuBr₃- Complex Studied with Sub-20 fs Resolution. / Khvorost, Taras A; Beliaev, Leonid Yu; Masaoka, Yuto et al.
In: Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, Vol. 125, No. 26, 2021, p. 7213-7221.

Research output: Contribution to journal › Journal article › Research › peer-review

TY - JOUR

T1 - Ultrafast Excited-State Dynamics of CuBr3- Complex Studied with Sub-20 fs Resolution

AU - Khvorost, Taras A

AU - Beliaev, Leonid Yu

AU - Masaoka, Yuto

AU - Hidaka, Tsubasa

AU - Myasnikova, Olesya S

AU - Ostras, Alexey S

AU - Bogachev, Nikita A

AU - Skripkin, Mikhail Yu

AU - Panov, Maxim S

AU - Ryazantsev, Mikhail N

AU - Nagasawa, Yutaka

AU - Mereshchenko, Andrey S.

PY - 2021

Y1 - 2021

N2 - Ultrafast excited-state dynamics of CuBr3- complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr3- complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr3- complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr3- complex exists as [CuBr3(CH3CN)2]-, whereas three forms of this complex, [CuBr3CH2Cl2]-, [CuBr3(CH2Cl2)2]-, and [CuBr3(CH2Cl2)3]-, are present in equilibrium in dichloromethane.

AB - Ultrafast excited-state dynamics of CuBr3- complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr3- complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr3- complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr3- complex exists as [CuBr3(CH3CN)2]-, whereas three forms of this complex, [CuBr3CH2Cl2]-, [CuBr3(CH2Cl2)2]-, and [CuBr3(CH2Cl2)3]-, are present in equilibrium in dichloromethane.

U2 - 10.1021/acs.jpcb.1c03797

DO - 10.1021/acs.jpcb.1c03797

M3 - Journal article

C2 - 34170695

SN - 1520-6106

VL - 125

SP - 7213

EP - 7221

JO - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

JF - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

IS - 26