The intersystem crossing (ISC) pathways of triplet benzene molecules in a benzene crystal were investigated theoretically. A combination of the gradient projection (GP) method, which is a standard method for optimizing the crossing seam of two potential energy surfaces, and the single-component artificial-force-induced reaction (SC-AFIR) method (GP/SC-AFIR) was used. This is the first reported use of a GP/SC-AFIR calculation using a density functional theory calculation with periodic boundary conditions. A systematic search for the minimum-energy structures in the seams of crossing of the singlet (S0) and triplet (T1) potential energy surfaces (S0/T1-MESX structures) found 39 independent S0/T1-MESX structures. Energy barriers between the S0/T1-MESX and the stationary structure of the triplet state (T1-MIN) were computed, and then two competing ISC pathways were extracted; the calculated overall energy barrier to the intermolecular C–C-bonded type (SX3) and the out-of-plane bent C–H type (SX15) S0/T1-MESX structures from T1-MIN were 0.26 and 0.27 eV, respectively. The rate constants for SX3 and SX15 formation were estimated to be 5.07 × 108 and 2.17 × 108 s−1 (at 273 K), respectively, or 9.73 × 10−5 and 4.78 × 10−6 s−1 (at 77 K), respectively. At 273 K, which is close to the melting point of the benzene crystal (278.5 K), SX3 and SX15 are easily accessible from T1-MIN, and ISC could occur through the S0/T1-MESX points. By contrast, at 77 K, T1-MIN survives long enough for phosphorescence to compete with ISC.
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21 August 2018
Research Article|
July 02 2018
Exploring potential crossing seams in periodic systems: Intersystem crossing pathways in the benzene crystal
Special Collection:
Enhanced Sampling for Molecular Systems
Kenichiro Saita;
Kenichiro Saita
a)
1
Department of Chemistry, Faculty of Science, Hokkaido University
, Sapporo 060-0810, Japan
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Makito Takagi;
Makito Takagi
2
Graduate School of Chemical Sciences and Engineering, Hokkaido University
, Sapporo 060-8628, Japan
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Yu Harabuchi;
Yu Harabuchi
1
Department of Chemistry, Faculty of Science, Hokkaido University
, Sapporo 060-0810, Japan
3
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST)
, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
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Haruki Okada;
Haruki Okada
1
Department of Chemistry, Faculty of Science, Hokkaido University
, Sapporo 060-0810, Japan
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Satoshi Maeda
Satoshi Maeda
a)
1
Department of Chemistry, Faculty of Science, Hokkaido University
, Sapporo 060-0810, Japan
4
Research and Services Division of Materials Data and Integrated System (MaDIS), National Institute for Materials Science (NIMS)
, Tsukuba 305-0044, Japan
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J. Chem. Phys. 149, 072329 (2018)
Article history
Received:
February 06 2018
Accepted:
June 11 2018
Citation
Kenichiro Saita, Makito Takagi, Yu Harabuchi, Haruki Okada, Satoshi Maeda; Exploring potential crossing seams in periodic systems: Intersystem crossing pathways in the benzene crystal. J. Chem. Phys. 21 August 2018; 149 (7): 072329. https://doi.org/10.1063/1.5025023
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