Second-order coherence

Figure 1.45 Coherence transfer pathways in 2D NMR experiments. (A) Pathways in homonuclear 2D correlation spectroscopy. The first 90° pulse excites singlequantum coherence of order p= . The second mixing pulse of angle /3 converts the coherence into detectable magnetization (p= —1). (Bra) Coherence transfer pathways in NOESY/2D exchange spectroscopy (B b) relayed COSY (B c) doublequantum spectroscopy (B d) 2D COSY with double-quantum filter (t = 0). The pathways shown in (B a,b, and d) involve a fixed mixing interval (t ). (Reprinted from G. Bodenhausen et al, J. Magn. Resonance, 58, 370, copyright 1984, Rights and Permission Department, Academic Press Inc., 6277 Sea Harbor Drive, Orlando, Florida 32887.)...

Figure 6.1 Nonlinear optical responses, (a) Second-order SF generation, the transition probability is enhanced when the IR light is resonant to the transition from the ground state g to a vibrational excited state V. CO is the angular frequency of the vibration, (b) Third-order coherent Raman scheme, the vibrational coherence is generated via impulsive stimulated...

Figure 13 Timing diagram for the clean HMBC experiment with an initial second-order and terminal adiabatic low-pass 7-filter.42,43 The recommended delays for the filters are the same than for a third-order low-pass J filter. <5 and 8 are gradient delays, where 8 — <5 + accounts for the delay of the first point in the 13C dimension. The integral over each gradient pulse G, is H/2yc times the integral over gradient G2 in order to achieve coherence selection. The recommended phase cycle is c/)n = x, x, x, x 3 — 4(x), 4(y), 4( x), 4(—y) with the receiver phase c/)REC = x, x.

Recently a new type of proton assisted recoupling experiments has been developed for coherence transfer where rf irradiation is taking place on all involved rf channels. This embraces the homonuclear proton assisted recoupling (PAR) [45, 140, 141] and the later resonant second-order transfer (RESORT) [142] experiments, as well as the heteronuclear proton assisted insensitive nuclei (PAIN) cross polarization [44] experiments. In PAR and PAIN, spin-lock CW irradiation is applied on both passive ( H) and active spins (13C, 15N) without matching rotary resonance conditions. In RESORT a phase alternation irradiation scheme for the passive spins is used. 

If j Rf is exactly the magic angle and infinite spinning speed is assumed, the first-order anisotropic terms are zero for both single and DQ coherence (33). This does not hold true for finite spinning speed, but a complete averaging of the first-order effect occurs at the exact rotor cycles. Therefore, the x evolution time has to match exactly a multiple of the rotor period. The second-order anisotropy refocusing occurs for... 

Experimental verification of the ISRS generation can be primarily given by the pump polarization dependence. The coherent phonons driven by ISRS (second order process) should follow the symmetry of the Raman tensor, while those mediated by photoexcited carriers should obey the polarization dependence of the optical absorption (first order process). It is possible, however, that both ISRS and carrier-mediated generations contribute to the generation of a single phonon mode. The polarization dependence is then described by the sum of the first- and second-order processes [20-22], as shown in Fig. 2.3. 

The SH intensity is proportional to P 2. Experimentally, the oscillatory part of the total SH is so small that one can ignore its second-order term. If coherent surface phonons are created by ISRS, the whole process including excitation and detection is the coherent time-domain analogue of stimulated hyper Raman scattering (y(4) process) [14]. The cross section of the SHG process is then proportional to the product of a Raman tensor in the pump transition and a hyper-Raman tensor dx k/dQn in the probe transition. 

The same equations, albeit with damping and coherent external driving field, were studied by Drummond et al. [104] as a particular case of sub/second-harmonic generation. They proved that below a critical pump intensity, the system can reach a stable state (field of constant amplitude). However, beyond the critical intensity, the steady state is unstable. They predicted the existence of various instabilities as well as both first- and second-order phase transition-like behavior. For certain sets of parameters they found an amplitude self-modula-tion of the second harmonic and of the fundamental field in the cavity as well as new bifurcation solutions. Mandel and Erneux [105] constructed explicitly and analytically new time-periodic solutions and proved their stability in the vicinity of the transition points. 

The other common technique used for determination of second-order NLO properties is second harmonic generation. In an SHG measurement a laser beam at frequency co illuminates a sample and coherent light at twice the frequency (2co) is generated and detected. These measurements can be performed on a wide range of sample types including powders in addition to those mentioned above for the LEO measurements. SHG is therefore a very useful method for... 

E. Brandas, C.A. Chatzidimitriou-Dreismann, On the Connection Between Certain Properties of the Second-Order Reduced Density Matrix and the Occurrence of Coherent-Dissipative Structures in Disordered Condensed Matter, Int. J. Quant. Chem. 40 (1991) 649. 

According to Section IV.A.3, for each wave vector K such that gcTK > A , there is an imaginary solution of (4.25). Thus, since localized states have a projection on every K> state, a very fast photon emission occurs (coherent emission) in the direction determined by K. In second-order perturbation theory124 126 (Fermi s golden rule"), / K takes values between 0 and x for... 

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