Plasmonic Trimers for Dual-Frequency Surface-Enhanced Two-Dimensional Infrared Spectroscopy
Plasmonic Trimers for Dual-Frequency Surface-Enhanced Two-Dimensional Infrared Spectroscopy
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用于双频表面增强二维红外光谱的等离子体三聚体
DOI：
10.1021/acs.jpcc.9b07045
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Chuntonov, Lev
中科院分区：
文献类型：
--
作者：
Mackin, Robert T.;Cohn, Bar;Engelman, Ben;Goldner, Adi;Rubtsov, Igor V.;Chuntonov, Lev
将表面增强二维红外光谱 (SE-2DIR) 扩展到双频实验，可以通过标记和探测分子不同位点的振动模式来研究分子薄膜中的动力学和能量传输。涉及由 SE-2DIR 在频率上很大程度上分离的跃迁的交叉峰的测量需要在相应频率下具有共振激发的等离子体纳米结构，其中相关的增强近场在空间上重叠，并且不同分子跃迁在同一分子中同时增强。金三聚体红外天线将增强场定位在其臂形成的间隙内。我们利用三聚体天线的对称性来单独调整面内等离子体激发的频率，以匹配感兴趣的分子跃迁。双频 SE-2DIR 测量在 4-叠氮基丁酸酯-N-羟基琥珀酰亚胺酯上进行了演示，其中羰基和叠氮伸缩振动模式之间的交叉峰（相距 370 cm-1）以及羰基和 C-N-C 伸缩振动模式（相距 550 cm-1）之间的交叉峰。使用交叉偏振激光脉冲的激发允许与选择性地访问相关分子跃迁共振的适当等离激元激发。我们的方法基于合理的等离子体激元模式工程，实现了涉及很大程度上分离的过渡频率的交叉峰值信号的显着增强，这是单宽带等离子体激元模式不可能实现的。
Extension of surface-enhanced two-dimensional infrared spectroscopy (SE-2DIR) to dual-frequency experiments allows studying dynamics and energy transport in thin molecular films by tagging and probing vibrational modes on different sites of the molecule. Measurements of cross-peaks involving transitions largely separated in frequency by SE-2DIR require plasmonic nanostructures with resonant excitations at the corresponding frequencies, where the associated enhanced near-fields spatially overlap and different molecular transitions are simultaneously enhanced in the same molecule. Gold trimer infrared antennas localize enhanced fields within the gap formed by their arms. We exploit the symmetry of trimer antennas to individually tune frequencies of the in-plane plasmonic excitations to match molecular transitions of interest. Dual-frequency SE-2DIR measurements are demonstrated on 4-azidobutyrate-N-hydroxysuccinimide ester with the cross-peaks between the carbonyl and azido stretching vibrational modes, separated by 370 cm–1, and the carbonyl and C–N–C stretching modes, separated by 550 cm–1. Excitation with cross-polarized laser pulses allows appropriate plasmon excitations in resonance with the relevant molecular transitions to be selectively accessed. Our approach, based on the rational plasmon mode engineering, achieves significant enhancement of the cross-peak signals involving largely separated transition frequencies, which is not possible with single broadband plasmon modes.
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氢键的双频 2D 红外光子回波
DOI：
10.1007/3-540-27213-5_164
发表时间：
2004
期刊：
Springer series in chemical physics
影响因子：
--
作者：
I. Rubtsov;Keshav Kumar;R. Hochstrasser
通讯作者：
R. Hochstrasser
影响因子：
5.7
作者：
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影响因子：
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Rubtsov, Igor V.
影响因子：
17.1
作者：
Neubrech, Frank;Weber, Daniel;Haertling, Thomas
通讯作者：
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影响因子：
3.8
作者：
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通讯作者：
J. Owrutsky