Phenol-water(1<or=n<or=3) revisited: an ab initio study on the photophysics of these clusters at the level of coupled cluster response theory.
The S1(pi*<--pi) state surfaces of the phenol-water(1<or=n<or=3) clusters are reexplored at the level of coupled cluster response theory. The global minima for n=2 and n=3 so obtained are qualitatively different from those reported so far, which were obtained with methods such as configuration interaction singles or complete active space self-consistent field lacking dynamical electron correlation effects. Furthermore, the minimum-energy points on the conical intersection seams were located in this work. The results of these calculations offer a qualitative explanation for the anomalous photophysical behavior (broad congested absorption band structure, low quantum yield, short lifetime) of n=2 and the observed predissociation of n=3 at excess energies beyond approximately 100 cm(-1), resolving a disagreement between theory and experiment which persisted for almost a decade.
Schemmel
Dominik
D
Institute of Physical and Theoretical Chemistry, University of Regensburg, Universitätsstrasse 31, D-93040 Regensburg, Germany.
Schütz
Martin
M
D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008962:Models, Theoretical; D008968:Molecular Conformation; D009991:Oscillometry; D010100:Oxygen / Q000737:chemistry; D019800:Phenol / Q000737:chemistry; D010777:Photochemistry / Q000379:methods*; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013053:Spectrophotometry; D014867:Water / Q000737:chemistry
D012997:Solvents; D014867:Water; D019800:Phenol; D006859:Hydrogen; D010100:Oxygen