Difference between heartwood and sapwood
Forest Products Laboratory (U.S.)
1919
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We report an excitation energy dependence of the dynamics of the excited-state intramolecular double-proton transfer of [2,2'-bipyridyl]-3,3'-diol in liquid solution. By means of femtosecond fluorescence upconversion experiments it is shown that an increase of the vibrational energy in the excited electronic S-1 state results in an increase of the ratio of the reaction yields of the monoketo and diketo tautomeric products. The dominance of the concerted double-proton transfer process at the lower excitation energies is evidence for an energy barrier in the dienol-monoketo reaction pathway.
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Abstract:
We have unraveled the effects of an amino substituent in the ortho position on the excited-state dynamics of 4-nitropyridine N-oxide by studying the picosecond fluorescence kinetics and femtosecond transient absorption of a newly synthesized compound, 2-butylamino-6-methyl-4-nitropyridine N-oxide, and by quantum chemical calculations. Similar to the parent compound, the S1 state of the target molecule has significant charge-transfer character and shows a large (~8000 cm-1) static Stokes shift in acetonitrile. Analysis of the experimental and the theoretical results leads, however, to a new scenario in which this intramolecular charge transfer triggers in polar, aprotic solvents an ultrafast (around 100 fs) intramolecular proton transfer between the amino and the N-O group. The electronically excited N-OH tautomer is subsequen...
The principal result in this paper is concerned with the derivative of a vector with respect to a block vector or matrix. This is applied to the asymptotic Fisher information matrix (FIM) of a stationary vector autoregressive and moving average time series process (VARMA). Representations which can be used for computing the components of the FIM are then obtained. In a related paper [A. Klein, A generalization of Whittle's formula for the information matrix of vector mixed time series, Linear Algebra Appl. 321 (2000) 197-208], the derivative is taken with respect to a vector. This is obtained by vectorizing the appropriate matrix products whereas in this paper the corresponding matrix products are left unchanged.
