Intensified C≡C Stretching Vibrator and Its Potential Role in Monitoring Ultrafast Energy Transfer in 2D Carbon Material by Nonlinear Vibrational Spectroscopy
| Autor: | Yanhuan Chen, Jian-Ping Wang, Huibiao Liu, Pengyun Yu, Juan Zhao, Yuliang Li, Yanzhou Wu |
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| Rok vydání: | 2019 |
| Předmět: |
0303 health sciences
Materials science Trimethylsilyl Infrared 030303 biophysics Infrared spectroscopy Hyperconjugation 03 medical and health sciences Dipole chemistry.chemical_compound chemistry Chemical physics Picosecond Intramolecular force General Materials Science Physical and Theoretical Chemistry Spectroscopy |
| Zdroj: | The Journal of Physical Chemistry Letters. 10:1402-1410 |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/acs.jpclett.9b00027 |
| Popis: | In this work, an intensity-enhanced C≡C stretching infrared (IR) absorption is observed in hexakis[(trimethylsilyl)ethynyl]benzene (HTEB), whose IR transition dipole magnitude becomes comparable to that of a typical C═O stretch, and the enhancement is believed to be due to a joint effect of π-π conjugation and hyperconjugation associated with a terminal trimethylsilyl group. Using dynamical time-dependent two-dimensional infrared (2D IR) spectroscopy, a picosecond intramolecular energy redistribution process is observed between two nondegenerate C≡C stretching modes, whose symmetry breaking is attributed to a noncovalent halogen-bonding interaction between HTEB and solvent CH2Cl2. The rigid structure of HTEB and limited structural dynamics are also inferred from the insignificant initial spectral diffusion value extracted from the 2D IR spectra. This work provides the first nonlinear infrared investigation of the conventionally weak C≡C stretch. The methods outlined are particularly important for detailed understanding of the structure-related processes such as vibrational energy transfer in novel C≡C species containing materials such as graphdiyne. |
| Databáze: | OpenAIRE |
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