From angle-action to Cartesian coordinates: A key transformation for molecular dynamics

The transformation from angle-action variables to Cartesian coordinates is a crucial step of the (semi) classical description of bimolecular collisions and photo-fragmentations. The basic reason is that dynamical conditions corresponding to experiments are ideally generated in angle-action variables whereas the classical equations of motion are ideally solved in Cartesian coordinates by standard numerical approaches. To our knowledge, the previous transformation is available in the literature only for triatomic systems. The goal of the present work is to derive it for polyatomic ones.Comment: 10 pages, 11 figures, submitted to J. Chem. Phy

Picosecond spectroscopy of electronically excited singlet states in biphenylene

A photophys. properties of biphenylene-h8 and biphenylene-d8 in soln. at room temp. was investigated with picosecond absorption and fluorescence spectroscopy. The weak fluorescence with complex vibrational structure originates entirely from the S1 state. It decays monoexponentially with a lifetime of 240 +- 20 ps. Upon photoexcitation to S2 no emission attributable to the S2 state was obsd. Lifetime and quantum yield of fluorescence (FF = 2.3 * 10-4) are the same for biphenylene-h8 and for the completely deuterated compd., indicating the C-H vibrations are not involved in the major radiationless decay process of the S1 level, i.e. internal conversion (jIC > 0.99). This conclusion is supported by INDO/S CI calcns. where strong changes of the CC bond orders (particularly in the central C4 ring) with S0 -> S1 excitation are found. The time-resolved excited-state absorption, measured at several wavelengths, decays biexponentially with time consts. of 8 +- 3 and 250 +- 40 ps. Various interpretations of the 8 ps lifetime are discussed; the conclusion results that the 8 ps transient has to be assigned to the lifetime of the S2 state even though the emission expected for an allowed transition with such a long lifetime is not obsd. Strong S1 -> Sn and S2 -> Sn excited-state absorption is found as predicted by INDO/S calcns

Experimental and theoretical studies of the thermal degradation of a phenolic dibenzodioxocin lignin model

International audienceA large part of biphenyl structures in lignin are etherified by alpha- and beta-carbons of another phenylpropane unit to give an eight-member ring called dibenzodioxocin. The behavior of a phenolic dibenzodioxocin lignin model, 4-(4,9-dimethoxy-2,11-n-dipropyl-6,7-dihydro-5,8-dioxa-dibenzo[a,c]cycloocten-6-yl)-2-methoxyphenol (DBDOH, 1), was studied by different mass spectrometry and thermal methods, leading to the conclusion that dibenzodioxocins are thermally unstable products. Both semi-empirical and density functional theory quantum calculations show that both C-O bonds, which connect the biphenyl part of the dibenzodioxocin molecule to the phenolic group, can be broken under increasing temperature. However, they do not play the same role since their dissociation occurs through different barrier heights. The C-O bond directly connected to the phenolic group (alpha-O-4) will dissociate first since its barrier energy for scission is lower than the other one (beta-O-4), by roughly 12 kcal mol(-1) (a parts per thousand 50 kJ mol(-1)). This conclusion is likely applicable to thermal degradation of DBDO units in lignin polymer