Vibrational Sum Frequency Generation by the Quadrupolar Mechanism at the Nonpolar Benzene/Air Interface

Matsuzaki, Korenobu; Nihonyanagi, Satoshi; Yamaguchi, S.; Nagata, Takashi; Tahara, Tahei

doi:10.1021/jz400829k

Cited by 51 publications

(54 citation statements)

References 19 publications

(25 reference statements)

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“…[16][17][18] Multiplex HD-SFG developed by the Tahara group takes advantage of multichannel detection using a femtosecond broad-band IR pulse, a polychromator, and a CCD. 22,31,[33][34][35][36][37][38][39][40][41][42] Interference fringes between SF signal and LO lights are recorded in the frequency domain. In this sense, interferometric and spectrometric measurements are both benefited by the multichannel detection in multiplex HD-SFG, which effectively reduces measurement time.…”

Section: Introductionmentioning

confidence: 99%

Development of single-channel heterodyne-detected sum frequency generation spectroscopy and its application to the water/vapor interface

Yamaguchi

2015

The Journal of Chemical Physics

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Single-channel heterodyne-detected sum frequency generation (HD-SFG) spectroscopy for selectively measuring vibrational spectra of liquid interfaces is presented. This new methodology is based on optical interference between sum frequency signal light from a sample interface and phase-controlled local oscillator light. In single-channel HD-SFG, interferometric and spectrometric measurements are simultaneously carried out with an input IR laser scanned in a certain wavenumber range, which results in a less task than existing phase-sensitive sum frequency spectroscopy. The real and imaginary parts of second-order nonlinear optical susceptibility (χ((2))) of interfaces are separately obtained with spectral resolution as high as 4 cm(-1) that is approximately six times better than existing multiplex HD-SFG. In this paper, the experimental procedure and theoretical background of single-channel HD-SFG are explicated, and its application to the water/vapor interface is demonstrated, putting emphasis on the importance of a standard for the complex phase of χ((2)).

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Section: Introductionmentioning

confidence: 99%

Development of single-channel heterodyne-detected sum frequency generation spectroscopy and its application to the water/vapor interface

Yamaguchi

2015

The Journal of Chemical Physics

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112

124

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“…This interfacial system has been investigated recently by different groups using SFVS. Benzene molecules are nonpolar, but their CH stretch vibrations can be readily observed by reflected SFVS from the air/benzene interface (21,24). Allen and coworkers interpreted the observed spectra as originating from the interfacial layer due to broken The EQ nonlinear susceptibility generally consists of two parts: one from EQ polarizability of individual molecules and the other from the phase retardation effect of induced dipoles on spatially distributed molecules.…”

Section: Resultsmentioning

confidence: 99%

“…The bulk contribution of benzene, being a nonpolar liquid, is expected to be strong, whereas the surface contribution from broken inversion symmetry could be weak. Reflected SFVS of the air/benzene interface has been reported by others (21)(22)(23)(24), but interpretations of the observed spectra are questionable considering that their reflected SF spectra always contain mixed surface and bulk contributions, thus providing no true surface spectrum.…”

mentioning

confidence: 89%

Surface sum-frequency vibrational spectroscopy of nonpolar media

Sun

Tian

Shen

2015

Proc. Natl. Acad. Sci. U.S.A.

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Sum-frequency generation spectroscopy is surface specific only if the bulk contribution to the signal is negligible. Negligible bulk contribution is, however, not necessarily true, even for media with inversion symmetry. The inevitable challenge is to find the surface spectrum in the presence of bulk contribution, part of which has been believed to be inseparable from the surface contribution. Here, we show that, for nonpolar media, it is possible to separately deduce surface and bulk spectra from combined phase-sensitive sum-frequency vibrational spectroscopic measurements in reflection and transmission. The study of benzene interfaces is presented as an example.sum-frequency spectroscopy | surface structure | bulk contribution | electric-quadrupole contribution | nonpolar media S um-frequency vibrational spectroscopy (SFVS) has been established as a powerful and versatile tool for studies of surfaces and interfaces of media with inversion symmetry (1-6). It is based on the idea that under the electric-dipole (ED) approximation, the bulk response for SF generation vanishes, but the surface response is necessarily nonvanishing because of the broken inversion symmetry at the surface. However, beyond the ED approximation, the bulk response is generally nonvanishing (7,8). In using SFVS as a surface probe, one must always worry whether the bulk response is negligible or can be distinguished from the surface response. In many publications on SFVS studies of an interface, however, the bulk response is simply ignored. A few papers have appeared to theoretically and experimentally describe how the surface and bulk responses may or may not be separately deduced from measurement (9-18),* , † but they do not seem to have clarified the situation. The conclusion from a more rigorous theory is that part of the bulk response is intrinsically inseparable from the surface response if surface and bulk resonances are not clearly different (19). However, as we shall show in this paper, separate deduction of surface and bulk spectra is possible for nonpolar media from properly designed reflection and transmission SFVS measurements. Using benzene as a test case, we present, to our knowledge, the first real surface spectrum of a neat liquid. The results also provide guidelines on when bulk contribution may be significant in applications of SFVS to surface studies.We begin with a brief review on the various physical mechanisms that contribute to SF generation (SFG) from an interfacial system (20). We consider a system formed by two semi-infinite isotropic media. SFG from the system in transmission or reflection measures a corresponding effective surface nonlinear susceptibility χ ! ð2Þ S,eff , which has contributions from four different physical origins: (i) An ED contribution from the interfacial layer due to broken inversion symmetry. (ii) An electric-quadrupole (EQ) contribution from the rapid field variation at the interface. (iii) An EQ contribution from the bulk. (iv) An EQ contribution from the bulk intrinsically inseparable fr...

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“…In the literature, the comparison between surface and bulk terms has been extensively studied for SHG, 49,50 but less so for SFG. 4,[51][52][53][54][55][56][57] There are two ways to describe the bulk contributions from an isotropic medium. The first one is inspired from the original work of Bloembergen and Pershan, 29 separating the nonlinear polarization inside the bulk into components parallel and perpendicular to the source wavevector q vis + q IR .…”

Section: A Nonlinear Optical Response Of Metal Surface and Bulk In Sfgmentioning

confidence: 99%

Determining nonlinear optical coefficients of metals by multiple angle of incidence heterodyne-detected sum-frequency generation spectroscopy

Yang

Busson

Hore

2020

The Journal of Chemical Physics

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We illustrate a technique by which heterodyne-detected sum-frequency generation spectroscopy is performed at multiple angles of incidence in order to decompose components of the second-order susceptibility tensor when all beams are polarized parallel to the plane of incidence. As an illustration we study the non-vibrationally resonant gold response. We benchmark our results by comparing with measurements obtained in a polarization scheme that isolates a single element of the susceptibility tensor. Our technique is particularly valuable in the case of metal substrates, where the surface selection rule often prevents spectra from being acquired in multiple beam polarizations.

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Vibrational Sum Frequency Generation by the Quadrupolar Mechanism at the Nonpolar Benzene/Air Interface

Cited by 51 publications

References 19 publications

Development of single-channel heterodyne-detected sum frequency generation spectroscopy and its application to the water/vapor interface

Development of single-channel heterodyne-detected sum frequency generation spectroscopy and its application to the water/vapor interface

Surface sum-frequency vibrational spectroscopy of nonpolar media

Determining nonlinear optical coefficients of metals by multiple angle of incidence heterodyne-detected sum-frequency generation spectroscopy

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