Theoretical investigation of two model systems for molecular photoswitch functionality. I. 2-(4-nitropyrimidin-2-yl)ethenol

Clemens Woywod, András Csehi, G. Halász, Kenneth Ruud, A. Vibók

Research output: Contribution to journalArticle

Abstract

The ground and five lowest-lying electronically excited singlet states of 2-(4-nitropyrimidin-2-yl)ethenol (NPE) have been studied theoretically using the complete active space self-consistent-field (CASSCF), Møller-Plesset second-order perturbation theory (MP2) and second-order multi-configurational perturbation theory (CASPT2) methods. The molecule can be regarded as being composed of a frame and a crane component and is characterised by the existence of two planar minima of similar energy on the ground-state potential energy (PE) surface. This work explores the possibility of an excited-state intramolecular hydrogen transfer (ESIHT) process in NPE. A hypothetical reaction coordinate has been constructed for NPE. State-averaged CASSCF and CASPT2 calculations of the six lowest-lying singlet states have been performed for the isomerisation. Adiabatic and simplified quasi-diabatic PE and transition dipole moment functions have been constructed. The computations indicate that there exist substantial barriers for the rotation process on the adiabatic PE surfaces of all the five excited states investigated. The six quasi-diabatic electronic states considered here decompose into two classes based on whether the electronic wave functions depend weakly or strongly on the nuclear displacement, subject to the effect of the torsion on relevant molecular orbitals.

Original languageEnglish
Pages (from-to)818-835
Number of pages18
JournalMolecular Physics
Volume112
Issue number5-6
DOIs
Publication statusPublished - Mar 19 2014

Fingerprint

Molecular Models
Excited states
Hydrogen
Potential energy surfaces
potential energy
self consistent fields
perturbation theory
excitation
cranes
Dipole moment
Electronic states
Molecular orbitals
Cranes
Wave functions
Isomerization
Potential energy
electronics
Torsional stress
Ground state
isomerization

Keywords

  • Electronic structure calculations
  • Excited state dynamics
  • Photoisomerisation
  • Photoswitch
  • Vibronic coupling

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Condensed Matter Physics
  • Biophysics
  • Molecular Biology

Cite this

Theoretical investigation of two model systems for molecular photoswitch functionality. I. 2-(4-nitropyrimidin-2-yl)ethenol. / Woywod, Clemens; Csehi, András; Halász, G.; Ruud, Kenneth; Vibók, A.

In: Molecular Physics, Vol. 112, No. 5-6, 19.03.2014, p. 818-835.

Research output: Contribution to journalArticle

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