Isomerization of stilbene in the gas phase: Theoretical study of isotopic and clustering effects

Abstract

Isotope effect in normal-to-local transition of acetylene bending modes J. Chem. Phys. 136, 014304 (2012); 10.1063/1.3673570Rotational isomerism of acetic acid isolated in rare-gas matrices: Effect of medium and isotopic substitution on IR-induced isomerization quantum yield and cis→trans tunneling rate This paper presents a continuation of our previous theoretical studies on the rate of isomerization of trans-stilbene from the first excited electronic state based on the potential energy surface of Vachev et al. ͓J. Phys. Chem. 99, 5247 ͑1995͔͒. Harmonic RRKM computations and molecular dynamics and Monte Carlo based classical rates are presented for deuterated isotopes of stilbene as well as hexane clusters of stilbene of varying size. Good agreement with experiment is found for energy dependent rates of d 12 vs h 12 stilbene. However, we find that the rate for d 2 stilbene is greater than for d 10 stilbene in contradiction to the experimental observations. For the hexane clusters we find that addition of hexane molecules causes a systematic decrease in the rate, in agreement with experiment.

Photoisomerization of Stilbene: The Detailed XMCQDPT2 Treatment

“…Numerous theoretical studies of stilbene ,,− include both quantum chemical studies and modeling of chemical dynamics by means of RRKM theory and its various modifications. However, only few works offer a sufficiently global study of the excited-state potential energy surface (PES).…”

Ab Initio Study of Cis−Trans Photoisomerization in Stilbene and Ethylene

“…We do not specifically address the barriers to ethylenic torsion which play a role in trans -stilbene photochemistry, nor the DHP reaction coordinate, which is a minor product channel for the cis isomer . The torsional barrier from the trans isomer is very important to the many studies which have used photoinduced isomerization of trans- stilbene in gas phase, cluster, and condensed phase environments as a benchmark system for studying statistical rate theories and intramolecular vibrational energy redistribution. − These details are left for future publication.…”

Viscosity dependence and solvent effects in the photoisomerization of cis-stilbene: Insight from a molecular dynamics study with an ab initio potential-energy function

“…[13][14][15][16] However, this procedure has little predictive power, since the desired results are put in previously, and then reproduced. Moreover, Eli Pollak and co-workers [17][18][19][20] apply sophisticated theories, based on transition state theory, to the photoisomerization of trans-stilbene. This reaction differs from cis-stilbene insofar that it is most probably thermally activated.…”