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Issue 40, 2007
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An examination of structural characteristics of phenylacetylene by vibronic and rovibronic simulations of ab initio data

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Abstract

The structural properties of phenylacetylene have been investigated in the S0(1A1) neutral ground and S1(1B2) and S2(1A1) singlet excited states and the D0(2B1) cationic state using both rovibronic and multidimensional Franck–Condon simulations from data determined via correlated ab initio methods. Results are compared to experimental and ab initio data reported in the literature. (10,10)-CASSCF and a hybrid CASSCF/SACCI frequency analysis using the cc-pVDZ Dunning basis set have been employed to produce vibronic simulations of REMPI/FES, dispersed fluorescence, TPES and MATI spectra. Calculated rotational constants are used where appropriate to compare to rotationally resolved experimental studies. Whilst the simulations are of generally good quality, it is apparent that the distortion of the ring along the long axis upon electronic excitation is underestimated, resulting in smaller predicted changes in ipso and para CCC bond angles and weaker activities in the 6a and 9a modes compared with experiment. Simulations of one-photon MATI spectra on the other hand, which do not rely on excited state methodologies, compare very well with experiment, suggesting that the neutral and cationic ground state geometries are quite accurate, as are the predicted changes in geometry accompanying ionisation. Simulated rotational and vibrational profiles, as well as other calculated physical data, show good agreement with the numerous experimental and computational studies of phenylacetylene in the literature.

Graphical abstract: An examination of structural characteristics of phenylacetylene by vibronic and rovibronic simulations of ab initio data

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Supplementary files

Article information


Submitted
05 Apr 2007
Accepted
31 Jul 2007
First published
20 Aug 2007

Phys. Chem. Chem. Phys., 2007,9, 5436-5445
Article type
Paper

An examination of structural characteristics of phenylacetylene by vibronic and rovibronic simulations of ab initio data

I. Pugliesi, N. M. Tonge, K. E. Hornsby, M. C. R. Cockett and M. J. Watkins, Phys. Chem. Chem. Phys., 2007, 9, 5436
DOI: 10.1039/B705194H

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