2016
DOI: 10.1073/pnas.1603080113
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Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations

Abstract: Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underl… Show more

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Cited by 47 publications
(94 citation statements)
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“…49,[67][68][69][70] In this context, particularly purposely tailored nanostructures such as nano-antennae or nano-slits with plasmon resonances located directly in the mid-IR spectral range have been shown to dramatically enhance IR absorbances. 67,[69][70][71][72][73][74] In that case, the quasi-static approximation, which we used in the derivation of Among the previous 2D IR investigations of Re-carbonyl complexes on various types of surfaces, 18,20,24,25,[38][39][40][41][42][43][44][45] the studies by Xiong et al 42,43 are the most closely related to our present report. That works has specifically looked at substrate-adsorbate interactions between an immobilized Re-complex and an underlying Au surface, suggesting that dipole/image-dipole interactions cause severe differences in lineshapes on the same molecule.…”
supporting
confidence: 52%
“…49,[67][68][69][70] In this context, particularly purposely tailored nanostructures such as nano-antennae or nano-slits with plasmon resonances located directly in the mid-IR spectral range have been shown to dramatically enhance IR absorbances. 67,[69][70][71][72][73][74] In that case, the quasi-static approximation, which we used in the derivation of Among the previous 2D IR investigations of Re-carbonyl complexes on various types of surfaces, 18,20,24,25,[38][39][40][41][42][43][44][45] the studies by Xiong et al 42,43 are the most closely related to our present report. That works has specifically looked at substrate-adsorbate interactions between an immobilized Re-complex and an underlying Au surface, suggesting that dipole/image-dipole interactions cause severe differences in lineshapes on the same molecule.…”
supporting
confidence: 52%
“…288–291 The sensitivity of 2D IR spectroscopy is also improving via technological and scientific advances. 292,293 Surface-enhanced 2D IR has been recently demonstrated using an ATR optical geometry. 294–296 Additionally, the combination of 2D IR with plasmonic nanostructures 297,298 promises to expand the technique’s impact by probing even smaller sample volumes and opening the door to vibrational modes with weaker oscillator strengths.…”
Section: Discussionmentioning
confidence: 99%
“…20 Since we however do not observe any direct cross peak, we assume that Eq. 3 overestimates the coupling, which is counter-balanced by the fact that cross-relaxation can proceed to more than one coupling partner on the surface (the model Despite significant efforts reported in literature 30,[47][48][49] , intermolecular couplings of surface-bound molecules have only rarely been observed 38 , and the estimates given above help to understand why that is so. In the present case, we can observe cross peaks with good signal-to-noise ratio, but this is since we have the very strong transition dipole of the symmetric stretch vibration of a metal-carbonyl together with (presumably) a close to optimal packing on the surface.…”
mentioning
confidence: 99%
“…Particularly for potentially catalytically-active systems, the ultrafast intramolecular vibrational dynamics of Re-carbonyl complexes in electronic ground and excited states have been investigated in detail before, mainly for bulk solution samples, but recently also for immobilized systems under a variety of experimental conditions. [37][38][39]45,47,48,50,52,[61][62][63][64][65] However, intermolecular dynamics are largely unexplored to date, since femtosecond multi-dimensional vibrational spectroscopy on surfaces became available only recently. 17,47,48,66 Nonetheless, it has been proposed that if the vibrational states of two molecules are coupled, the electronic states will be as well, which in turn may have a decisive impact on the performance of working devices.…”
mentioning
confidence: 99%