It is shown that the direct precursor for the formation of a photochrome in Schiff bases is a “twisted” geometry state of a keto tautomer in which the O⋯N–H hydrogen bond is broken. In photochromic Schiff bases this state is close in energy to the ππ* state of the cis-ketone obtained from the initially optically excited enol species by an ultrafast excited-state proton transfer, in particular, in N-salicylidene-α-methylbenzylamine (SMB), it lies within 1 kcal/mol from the ππ* state of cis-ketone and ∼16 kcal/mol below the initial ππ* state of enol. The excited-state proton transfer in SMB is predicted to take ∼15 fs and to be nearly barrierless. It is also shown that the initial ππ* state of enol can decay via competing route to a twisted geometry state of enol with the energy ∼20 kcal/mol below that state.
Skip Nav Destination
Article navigation
8 November 2001
Research Article|
November 08 2001
Theoretical study of photochromism of N-salicylidene-α-methylbenzylamine
Marek Z. Zgierski
Marek Z. Zgierski
Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa K1A 0R6, Canada
Search for other works by this author on:
J. Chem. Phys. 115, 8351–8358 (2001)
Article history
Received:
July 09 2001
Accepted:
August 24 2001
Citation
Marek Z. Zgierski; Theoretical study of photochromism of N-salicylidene-α-methylbenzylamine. J. Chem. Phys. 8 November 2001; 115 (18): 8351–8358. https://doi.org/10.1063/1.1411999
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
Theoretical approach to photochromism of aromatic Schiff bases: A minimal chromophore salicylidene methylamine
J. Chem. Phys. (November 2000)
Theoretical study of excited state proton transfer in 3,6-bis(benzoxazolyl)pyrocatechol (BBPC)
J. Chem. Phys. (May 2002)
Electronic-structure and quantum dynamical study of the photochromism of the aromatic Schiff base salicylideneaniline
J. Chem. Phys. (December 2008)
Ultrafast excited-state dynamics in photochromic N-salicylideneaniline studied by femtosecond time-resolved REMPI spectroscopy
J. Chem. Phys. (November 2004)
Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment
J. Chem. Phys. (January 2001)