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Proceedings of SPIE, the International Society for Optical Engineering/Proceedings of SPIE

Vibrational coherence of DCl in cryogenic matrices: from van der Waals interaction to weak hydrogen bond

Claudine Crépin, Michel Broquier, Arnaud Cuisset, Henri Dubost, Jean‐Pierre Galaup, Pascale Roubin, Jean Michel Ortega

Published Nov 1, 2002• 0 citations
Publisher

Abstract

The influence of the environment on vibrational dynamics, and especially on the vibrational dephasing time, is investigated for a simple system : DCl in a van der Waals solid (N2 lattice). Photon echo experiments are performed using the infrared free electron laser CLIO. In solid nitrogen, decay times of the third order polarization are in the picosecond range. In the case of the isolated DCl monomers in van der Waals interaction with the host, the observed signals are interpreted in term of a rapid spectral diffusion. The two different stretching modes of DCl dimers, perturbed in a different way by the weak hydrogen bond, exhibit different coherence times, reflecting the influence of the interaction strength between the molecules.

DOI
10.1117/12.455921

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Proceedings of SPIE, the International Society for Optical Engineering/Proceedings of SPIE•Apr 1, 1990•0 citations
The influence of the environment on vibrational dynamics, and especially on the vibrational dephasing time, is investigated for a simple system : DCl in a van der Waals solid (N2 lattice). Photon echo experiments are performed using the infrared free electron laser CLIO. In solid nitrogen, decay times of the third order polarization are in the picosecond range. In the case of the isolated DCl monomers in van der Waals interaction with the host, the observed signals are interpreted in term of a rapid spectral diffusion. The two different stretching modes of DCl dimers, perturbed in a different way by the weak hydrogen bond, exhibit different coherence times, reflecting the influence of the interaction strength between the molecules.
The dynamics in the ground electronic state of the two intramolecular D-Cl stretching modes of (DCl)2 in nitrogen solid has been probed by degenerate four wave mixing experiments. Accumulated photon echoes on the "free" nu1 and "bonded" nu2 modes have been performed by means of the free electron laser of Orsay (CLIO). The analysis of the time-resolved signals provides information on the various processes responsible for the loss of vibrational coherence, in particular intra- and intermolecular vibrational energy transfer and pure dephasing. The influence of the weak hydrogen bond is clearly observed on the coherence times of the two stretching modes. Whatever the temperature, the homogeneous width of nu2 lines is almost twice that of nu1 lines. Contrary to the case of isolated DCl trapped in solid nitrogen, no obvious effect of the nitrogen lattice can be extracted from the temperature dependence of the coherence times.
Explorer la dynamique vibrationnelle, dans l'etat electronique fondamental, de systemes pieges en matrice cryogenique est une approche pertinente pour decrire des interactions specifiques entre une molecule et son environnement. Cette dynamique vibrationnelle a ete sondee par des experiences d'echos de photons utilisant le Laser a Electrons Libres du Centre Laser Infrarouge d'Orsay. Ces experiences permettent d'une part de mesurer directement le temps de dephasage vibrationnel T2 extremement sensible aux interactions avec l'environnement et d'autre part, d'etudier la diffusion spectrale induite par les transferts d'energie vibrationnelle entre molecules piegees. Nous avons choisi un systeme simple et spectroscopiquement bien connu : DC1 piege en matrice qui nous permet, dans un meme echantillon, de tester differentes interactions. Dans l'azote solide, les echos de photons ont permis d'obtenir une description complete de la dynamique vibrationnelle du monomere DC1. Les resultats soulignent l'interaction non negligeable entre la vibration sondee et la matrice d'azote. Dans cette matrice, les signaux resolus en temps obtenus par excitation des dimeres et trimeres montrent une claire influence d'une liaison hydrogene faible sur la dynamique vibrationnelle. Par ailleurs, des experiences en matrice d'argon ont ete realisees en sondant principalement des especes (DCl)X complexees avec une ou plusieurs molecules d'azote. La comparaison avec les resultats en matrice d'azote permet de constater une forte difference entre les effets de complexation et les effets de solide sur la dynamique vibrationnelle.
Infrared picosecond accumulated photon echo experiments have been performed for the first time, using the Orsay Free Electron Laser, on the $v\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0\ensuremath{\rightarrow}v\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}1$ transition of CO in solid nitrogen. The vibrational dephasing time is found to be exceptionally long ( ${T}_{2}\ensuremath{\ge}120$ ns) at low temperature. The analysis of the observed spectral diffusion leads one to assume different energy transfer mechanisms depending on the CO concentration.
We present the first infrared photon echo study of liquid water. For the O-H stretch vibration of HDO in D2O{\mathrm{D}}_{2}\mathrm{O}D2​O, femtosecond four-wave mixing experiments reveal an extraordinary short pure dephasing time T2∗{T}_{2}^{*}T2∗​ on the order of 90 fs. This unusually fast time scale of dephasing is rationalized by taking into account the large anharmonicity of the hydrogen bonded O-H stretching mode.
Picosecond optical coherence techniques are employed to study dynamical intermolecular interactions in low concentration mixed molecular crystals, i.e., pentacene in naphthalene at 1.4 K. A concentration-dependent broadening of the optical homogeneous line is observed. Stimulated photon echo measurements rule out excited state transport as the broadening mechanism. The photon echo results exhibit a linear concentration dependence and a theory is proposed that accounts for the broadening in terms of phonon-induced fluctuations in guest–guest dipole–dipole interactions. Detailed considerations indicate that the system is best described in terms of localized excitations rather than delocalized impurity band states. In the low concentration limit, there is additional broadening of the homogeneous line beyond that produced by the lifetime. A model is presented describing this broadening in terms of phonon-induced modulation of the guest–host van der Waals interactions, i.e., in terms of a fluctuating crystal shift.
Picosecond photon echo (PE) experiments are used to examine the optical dephasing and intermolecular interactions of organic chromophores in a variety of glassy organic and polymer hosts. The inherent disorder in these systems leads to dynamics which span times from picoseconds to hours and longer. The temperature dependent optical dephasing as measured by the PE follows a power law characteristic of tunnelling twolevel systems (TLS) at low temperatures (1 °K to 4 °K) and is exponentially activated at higher temperatures due to dephasing by additional modes. The nature of these modes will be addressed. These data and those from other line narrowing experiments such as hole burning allow the study both of fast dephasing processes and spectral diffusion due to slow fluctuations in the host. The observed lineshapes and holewidths require dipolar coupling between the chromophore and TLS and offer information on the distribution of relaxation rates. Furthermore, techniques sensitive to different timescales are used to examine host dynamics by removing the guest-host coupling from consideration. The data are discussed in conjunction with recently developed theoretical treatments of dephasing in disordered systems.