Spectroscopy nonlinear

The inherent resolution of collinear-beam spectroscopy is still limited by the residual Doppler broadening. In beams with a broad velocity distribution the labeling of one velocity class by optical pumping, probed in a second Doppler-tuning zone, was exploited already before narrow Doppler widths were achieved. The complete elimination of the first-order Doppler effect in resonant two-photon absorption on Ne I has been discussed in Section 3.3, in connection with a precision measurement of the relativistic Doppler effect. A similar experiment was performed on In I, where the 29p Rydberg state was excited from 5p Pi/2 via 6s Si/2 and detected by field ionization. The linewidth caused by the laser jitter can be reduced to the transit-time limit of a few hundred kilohertz. 

Classical saturated absorption experiments on fast beams require different laser wavelengths to saturate and probe the same transition. However, a three-level system in V or A configuration can be realized to use the same direct and retroreflected laser beam interacting with the velocity class p under the condition 

One of the essential advantages that single-mode lasers can offer for high-resolution spectroscopy is the possibility of overcoming the limitation set by Doppler broadening. Several techniques have been developed that are based on selective saturation of atomic or molecular transitions by sufficiently intense lasers. 

The population density of molecules in the absorbing level is decreased by optical pumping. This results in a nonlinear dependence of the absorbed radiation power on the incident power. Such techniques are therefore summarized as nonlinear spectroscopy, which also includes methods that are based on the simultaneous absorption of two or more photons dining an atomic or molecular transition. In the following sections the basic physics and the experimental realization of some important methods of nonlinear spectroscopy are discussed. At first we shall, however, treat the saturation of population densities by intense incident radiation. 

---

This section begins with a brief description of the basic light-molecule interaction. As already indicated, coherent light pulses excite coherent superpositions of molecular eigenstates, known as wavepackets , and we will give a description of their motion, their coherence properties, and their interplay with the light. Then we will turn to linear and nonlinear spectroscopy, and, finally, to a brief account of coherent control of molecular motion. 

The pioneering use of wavepackets for describing absorption, photodissociation and resonance Raman spectra is due to Heller [12, 13,14,15 and 16]- The application to pulsed excitation, coherent control and nonlinear spectroscopy was initiated by Taimor and Rice ([17] and references therein). 

As described at the end of section Al.6.1. in nonlinear spectroscopy a polarization is created in the material which depends in a nonlinear way on the strength of the electric field. As we shall now see, the microscopic description of this nonlinear polarization involves multiple interactions of the material with the electric field. The multiple interactions in principle contain infomiation on both the ground electronic state and excited electronic state dynamics, and for a molecule in the presence of solvent, infomiation on the molecule-solvent interactions. Excellent general introductions to nonlinear spectroscopy may be found in [35, 36 and 37]. Raman spectroscopy, described at the end of the previous section, is also a nonlinear spectroscopy, in the sense that it involves more than one interaction of light with the material, but it is a pathological example since the second interaction is tlirough spontaneous emission and therefore not proportional to a driving field... 

There is an aspect of nonlinear spectroscopy which we have so far neglected, namely the spatial dependence of the signal. In general, tln-ee incident beams, described by /c-vectors k, k2 and will produce an outgoing beam at each of the directions ... 

A clear, comprehensive discussion of the many facets of nonlinear optics. The emphasis is on optical effects, such as hannonic generation. The treatment of nonlinear spectroscopy, although occupying only a fraction of the book, is clear and physically well-motivated. 

Lee D and Albrecht A C 1993 On global energy conservation in nonlinear light matter interaction the nonlinear spectroscopies, active and passive Adv. Phys. Chem. 83 43-87... 

Depending on the relative phase difference between these temis, one may observe various experimental spectra, as illustrated in figure Bl.5.14. This type of behaviour, while potentially a source of confiision, is familiar for other types of nonlinear spectroscopy, such as CARS (coherent anti-Stokes Raman scattering) [30. 31] and can be readily incorporated mto modelling of measured spectral features. 

Hicks J M, Petralli-Mallow T and Byers J D 1994 Consequences of chirality in second-order nonlinear spectroscopy at interfaces Faraday Disc. 99 341 -57... 

In this chapter we review some of the most important developments in recent years in connection with the use of optical teclmiques for the characterization of surfaces. We start with an overview of the different approaches available to tire use of IR spectroscopy. Next, we briefly introduce some new optical characterization methods that rely on the use of lasers, including nonlinear spectroscopies. The following section addresses the use of x-rays for diffraction studies aimed at structural detenninations. Lastly, passing reference is made to other optical teclmiques such as ellipsometry and NMR, and to spectroscopies that only partly depend on photons. 

A comprehensive theoretical treatment of nonlinear spectroscopy, with an emphasis on theory applicable to ultrafast nonlinear spectroscopy. 

Plakhotnik T, Walser D, Pirotta M, Renn A and Wild U P 1996 Nonlinear spectroscopy on a single quantum system two-photon absorption of a single molecule Science 271 1703-5... 

The simple fitting procedure is especially useful in the case of sophisticated nonlinear spectroscopy such as time domain CARS [238]. The very rough though popular strong collision model is often used in an attempt to reproduce the shape of pulse response in CARS [239]. Even if it is successful, information obtained in this way is not useful. When the fitting law is used instead, both the finite strength of collisions and their adiabaticity are properly taken into account. A comparison of... 

Letokhov V. S., Chebotayev V. P. Nonlinear Laser Spectroscopy. (Springer, Berlin) Springer Series in Optical Science (1977) [Principles of the Nonlinear Spectroscopy. (Nauka, Moscow) (1975)]. 

Webster S, Odom SA, Padilha LA, Przhonska OV, Peceli D, Hu H, Nootz G, Kachkovski AD, Matichak J, Barlow S, Anderson HL, Marder SR, Hagan DJ, Van Stryland EW (2009) Linear and nonlinear spectroscopy of a porphyrin-squaraine-porphyrin conjugated system. J Phys Chem B 113 14854-14867... 

Theoretical calculations for ultrafast neat water spectroscopy are difficult to perform and difficult to interpret (because of the near-resonant OH stretch coupling). One classical calculation of the 2DIR spectrum even preceded the experiments [163] Torii has calculated the anisotropy decay [97], finding reasonable agreement with the experimental time scale. Mixed quantum/ classical calculations of nonlinear spectroscopy for many coupled chromo-phores is a daunting task. We developed the TAA for linear spectroscopy, and Jansen has very recently extended it to nonlinear spectroscopy [164]. We hope that this will allow for mixed quantum/classical calculations of the 2DIR spectrum for neat water and that this will provide the context for a molecular-level interpretation of these complex but fascinating experiments. 

Lozovoy, V. V., Shane, J. C., Xu, B. W., and Dantus, M. 2005. Spectral phase optimization of femtosecond laser pulses for narrow-band, low-background nonlinear spectroscopy. Opt. Exp. 13(26) 10882-87. 

Unlike in bulk nonlinear spectroscopy experiments, the signal in nonlinear microscopy is generated within a volume that is on the order of an optical wavelength. The axial extent of this volume is often referred to as the interaction length, which denotes the length within which the incident fields interact to produce a nonlinear polarization in the material. Such microscopic interaction lengths yield signal interference profiles that can differ markedly from those observed in macroscopic spectroscopy. 

Biomolecular Imaging by Near-Field Nonlinear Spectroscopy and Microscopy... 

IV. COMBINATION OF TIP-ENHANCEMENT AND SECOND-ORDER NONLINEAR SPECTROSCOPY... 

Nonlinear spectroscopy study of vibrational self-trapping in hydrogen bonded crystals... 

---