The photoisomerization path and dynamics of trans–trans (ttD), cis–trans (ctD), and cis–cis (ccD) 1,4-diphenyl-1,3-butadiene (DPB) in solution are studied with broadband transient absorption (TA) spectroscopy and quantum chemical calculations. For ttD in n-hexane, 2-photon-excited TA spectra indicate that the 2Ag state is located above 1-photon allowed 1Bu (S1) by ∼1000 cm−1. Following S0 → S1 optical excitation, the isomerization occurs via torsion about a butadiene double bond to perpendicular molecular configuration P. The P-state is detected in ccD with an excited-state absorption band at 390 nm. This P-band develops during S1 → P half-torsion with time of 0.15 ps, followed further by P → S0 half-torsion and simultaneous decay with 1.6 ps in acetonitrile and 5 ps in n-hexane. In addition, two oscillation cycles between P and S1 population are observed before equilibration in n-hexane. For ctD, an indication of rising and decaying P is found in acetonitrile. The vast majority of ctD species photoisomerizes to ttD and not to ccD, in agreement a with calculated low torsional barrier about the cis double bond and high barrier about the trans double bond. Photoisomerization yield Y and time τi depend drastically on the solvent polarity. Thus, in n-hexane, the isomerization ttD → ctD has yield Ytt,ct = 0.1 and time τi = 829 ps, while in acetonitrile, Ytt,ct = 0.4 and τi = 27 ps. The 30-fold acceleration of the isomerization in acetonitrile clearly reflects a highly polar character of P, consistent with a dipole moment μP > 9.6 D. The results for DPB are discussed in comparison to stilbene.
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14 June 2020
Research Article|
June 11 2020
Photoisomerization dynamics of trans–trans, cis–trans, and cis–cis diphenylbutadiene from broadband transient absorption spectroscopy and calculations
O. A. Krohn
;
O. A. Krohn
1
JILA and the Department of Physics, University of Colorado
, Boulder, Colorado 80309, USA
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M. Quick
;
M. Quick
2
Department of Chemistry, Humboldt-Universität zu Berlin
, Berlin, Germany
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S. M. Sudarkova;
S. M. Sudarkova
3
Department of Chemistry, Lomonosov Moscow State University
, Moscow, Russia
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I. N. Ioffe;
I. N. Ioffe
a)
3
Department of Chemistry, Lomonosov Moscow State University
, Moscow, Russia
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C. Richter;
C. Richter
2
Department of Chemistry, Humboldt-Universität zu Berlin
, Berlin, Germany
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S. A. Kovalenko
S. A. Kovalenko
a)
2
Department of Chemistry, Humboldt-Universität zu Berlin
, Berlin, Germany
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O. A. Krohn
1
M. Quick
2
S. M. Sudarkova
3
I. N. Ioffe
3,a)
C. Richter
2
S. A. Kovalenko
2,a)
1
JILA and the Department of Physics, University of Colorado
, Boulder, Colorado 80309, USA
2
Department of Chemistry, Humboldt-Universität zu Berlin
, Berlin, Germany
3
Department of Chemistry, Lomonosov Moscow State University
, Moscow, Russia
J. Chem. Phys. 152, 224305 (2020)
Article history
Received:
March 10 2020
Accepted:
May 19 2020
Citation
O. A. Krohn, M. Quick, S. M. Sudarkova, I. N. Ioffe, C. Richter, S. A. Kovalenko; Photoisomerization dynamics of trans–trans, cis–trans, and cis–cis diphenylbutadiene from broadband transient absorption spectroscopy and calculations. J. Chem. Phys. 14 June 2020; 152 (22): 224305. https://doi.org/10.1063/5.0007241
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