TY - JOUR

T1 - Perylene-rare-gas heteroclusters. I. Electronic spectroscopy

AU - Bahatt, Dar

AU - Heidenreich, Andreas

AU - Ben-Horin, Narda

AU - Even, Uzi

AU - Jortner, Joshua

PY - 1994

Y1 - 1994

N2 - In this paper we report on the electronic two-photon two-color near threshold spectroscopy of mass-resolved perylene-Arn (n=1-45), perylene-Krn (n=1-35), perylene·(N2)n (n=1-12), and perylene·(CH4)n (n=1-10) heteroclusters. The S0→S1 inhomogeneously broadened spectra of perylene·Arn (n=1-6) and perylene·Kr n (n=1-4) exhibit resolved spectral features, which were assigned on the basis of experimental combination rules and polarizability relations to the electronic origins of distinct two-sided and one-sided structural isomers. Larger perylene·An (A=Ar, Kr; n=6-10) heteroclusters exhibit an "abnormal" specific size dependence of the red spectral shifts, which decrease with increasing n and reach a local minimum at n=8. Similar characteristics of the red spectral shifts are exhibited for perylene"(N2)n and perylene·(CH 4)n (n=4-8) heteroclusters. This abnormal size dependence of the spectral shifts is attributed to the dominance of one-sided single-layered and double-layered structural isomers in this cluster size domain. On the basis of the comparison between the spectroscopic data and molecular dynamics simulations of the absorption line shapes we have obtained a quantitative description of isomer-specific structures for n=2-6, a semiquantitative description of the abnormal size domain for n=6-10 (due to the dominance of one-sided structures with the abundance of two-layered structures increasing at higher n), the prevalence of one-sided structures for n=16 and n=22, and the realization of two-sided multilayered structures at n=45.

AB - In this paper we report on the electronic two-photon two-color near threshold spectroscopy of mass-resolved perylene-Arn (n=1-45), perylene-Krn (n=1-35), perylene·(N2)n (n=1-12), and perylene·(CH4)n (n=1-10) heteroclusters. The S0→S1 inhomogeneously broadened spectra of perylene·Arn (n=1-6) and perylene·Kr n (n=1-4) exhibit resolved spectral features, which were assigned on the basis of experimental combination rules and polarizability relations to the electronic origins of distinct two-sided and one-sided structural isomers. Larger perylene·An (A=Ar, Kr; n=6-10) heteroclusters exhibit an "abnormal" specific size dependence of the red spectral shifts, which decrease with increasing n and reach a local minimum at n=8. Similar characteristics of the red spectral shifts are exhibited for perylene"(N2)n and perylene·(CH 4)n (n=4-8) heteroclusters. This abnormal size dependence of the spectral shifts is attributed to the dominance of one-sided single-layered and double-layered structural isomers in this cluster size domain. On the basis of the comparison between the spectroscopic data and molecular dynamics simulations of the absorption line shapes we have obtained a quantitative description of isomer-specific structures for n=2-6, a semiquantitative description of the abnormal size domain for n=6-10 (due to the dominance of one-sided structures with the abundance of two-layered structures increasing at higher n), the prevalence of one-sided structures for n=16 and n=22, and the realization of two-sided multilayered structures at n=45.

UR - http://www.scopus.com/inward/record.url?scp=0000219545&partnerID=8YFLogxK

U2 - 10.1063/1.467091

DO - 10.1063/1.467091

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AN - SCOPUS:0000219545

SN - 0021-9606

VL - 100

SP - 6290

EP - 6299

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 9

ER -