Radiationless relaxation and optical dephasing of molecules excited by widehyphen; and narrowhyphen;band lasers. II. Pentacene in lowhyphen;temperature mixed crystals

摘要

One purpose of this paper is to present new studies on the effect of bandwidth and the coherence properties of the excitation source on the decay and the dephasing of isolated large molecules. A detailed study of the system pentacene in aphyphen;terphenyl matrix is presented utilizing three different excitation sources, a single mode dye laser (60 KHzndash;6 MHz bandwidth depending on the time scale of the experiment) a multimode dye laser (240 GHz bandwidth), and an incoherent N2flash lamp. OpticalT1(the longitudinal relaxation time) andT2(the transverse relaxation time) are measured from the coherent and incoherent transients observed either in the forward direction of the laser or at right angles to the exciting beam. At 1.8thinsp;deg;K, the optical transition (1A1grarr;1B2u) of pentacene inphyphen;terphenyl exhibits four sites, the lowest of which at 16thinsp;887 cmminus;1has the following parameters:T2=44plusmn;2 nsec;T1=24.9plusmn;2 nsec, and mgr;=0.7plusmn;0.1 D. The transition moment mgr;, is obtained directly from the optical nutation, which exhibits a Rabi nutation time (hslash;/mgr;sdot;egr;) of 27.3 nsec, and is corrected for the effect of the Lorentz local field inside the terphenyl crystal. The experiments presented here are categorized into two time regimes for theoretical analysis; atransientcoherenceregime where the observed decay is comparable with (hslash;/mgr;sdot;egr;) andT2, and asteadyhyphen;statecoherenceregime where transient dephasing is complete and the offhyphen;diagonal elements of the density matrix have decayed to their steadyhyphen;state values in the presence of the field of amplitude egr;. Using the Wilcoxndash;Lamb method, rate equations (withT2expressions) describing the population flow in the rsquo;rsquo;completersquo;rsquo; level structure of pentacene (groundVerbar;0rang;, singlet Verbar;prang;, and triplet lcub;Verbar;lrcub;) are derived from the density matrix equations of motion. When these equations are averaged over the inhomogeneous width of the optical transition and the measured Gaussian transverse profile of our laser we obtainT1p0=24.9plusmn;2 nsec andT1pl=15.7 mgr;sec, the time constants by which pentacene spontaneously decays to Verbar;0rang; or crosses over intol, as well as the averaged population at timet. In an effort to be complete, attention is placed upon the relationship between theory and the experimental findings. First, expressions for the OFID and nutation in the solid are presented for the pentacene case in order to relateT1,T2, and mgr; to the level structure. Second, at low temperatures (1.8thinsp;deg;K), the origin of dephasing is identified as spontaneous emission fromprarr;0 since experimentallyT2quest;2T1, in agreement with other work. At higher temperature, however, a strongly temperature dependent dephasing process with an onset at 3.7thinsp;deg;K takes place. Armed with these observations we present a theoretical treatment of these distinct dephasing channels and their temperature dependences. A discussion regarding the influence of rsquo;rsquo;acceptingrsquo;rsquo; phonon modes (either optical or acoustic) on optical dephasing is also given. The results indicate that the treatment of Jonesetal. can (1) explain the observed temperature dependence ofT2in pentacene; (2) distinguish dephasing as a result of scattering by acoustic phonons from that due to resonance or quasilocalized phonons with clear connections to gas and liquid state theories, but without invoking more than two approximation levels. (3) explain both the level shift and line width changes as a result of rsquo;rsquo;conventionalrsquo;rsquo; dephasing or dephasing by exchange mechanisms; and (4) relate the pure dephasing term to an anisotropy in the scattering amplitudes (between the ground and excited states in the system) which contribute largely to the homogeneous width of the transition. Optical site selection of these transitions is also reported and discussed in relation to vibrational relaxation and to both homogeneous and inhomogeneous broadenings. The studies of the homogeneous broadening of the vibronic origin (267 cmminus;1) indicate that vibrational relaxation is fast (psec) in the excited singlet manifold of pentacene. Finally from more than ten independent experiments including single and multimode excitation, onhyphen; and offhyphen;resonance scattering, Zeeman effect and the transient decay as a function of excess energy in the molecule, a more complete picture of the pentacene level structure lcub;Verbar;lrang;rcub; is given. With this in mind, the influence of the laser bandwidth and coherence properties on state preparation and subsequent dephasing and decay is concluded. It is proposed that the slow decay, (sim;15 mgr;sec) observed during narrowhyphen;band excitation represents intersystem crossing to nearby triple manifolds after the transient coherence of the 0harr;psubsystem is decayed. In addition, the decay of the primary state prepared in these experiments is not sensitive to the bandwidth or the correlation time of our excitation sources.