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Mode-selective photoisomerization in 5-hydroxytropolone. I. Experiment
Laser-induced fluorescence excitation, dispersed fluorescence, and population labeling spectra of the S0–S1 transition of 5-hydroxytropolone (5-HOTrOH) have been recorded in a supersonic free je...
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Mode-selective photoisomerization in 5-hydroxytropolone. II. Theory

J. Chem. Phys. 102, 5260 (1995); doi:10.1063/1.469251

Issue Date: 1 April 1995

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John J. Nash and Timothy S. Zwier
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393

Kenneth D. Jordan
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260
Ab initio calculations are used to explore the ground-state potential energy surface for the syn–anti photoisomerization reaction of 5-hydroxytropolone (5-HOTrOH). Two reaction coordinates are identified, involving 2-OH tunneling and 5-OH torsion. Hartree–Fock (HF) and perturbation theory (at the MP2 level) have been used to calculate the stationary points on the two-dimensional surface associated with these coordinates. Similar calculations on the parent molecule tropolone are carried out for comparison. As observed in previous studies, the 2-OH tunneling barrier drops dramatically at the MP2 level which includes electron correlation. Vibrational frequency calculations are carried out for both tropolone and 5-HOTrOH at the HF/6-31G** and MP2/6-31G** levels in order to correlate the modes with those observed experimentally. A method is introduced for evaluating which normal coordinates should be most strongly coupled to a given reaction coordinate. Normalized, mass-weighted intrinsic and direct reaction coordinates similar in form to the normal coordinates are devised by projecting atomic displacements from the reactant structure toward a transition state (intrinsic) or product (direct) structure. These serve as limiting cases for the initial projections of the multidimensional reaction trajectories. The intrinsic and direct reaction coordinates are then expanded in the basis set of normal coordinates to obtain coefficients of expansion of the reaction coordinates in this basis set. This simple scheme highlights the subset of normal coordinates which are important in promoting reaction by H-atom tunneling or O–H torsion. In 5-HOTrOH, an in-plane mode calculated at 348 cm−1 has a large coefficient of expansion along both intrinsic and direct reaction coordinates. This mode is assigned as the ``promoter mode'' W observed in the experimental study of paper I. ©1995 American Institute of Physics.
History: Received 7 October 1994; accepted 20 December 1994
Permalink: http://link.aip.org/link/?JCPSA6/102/5260/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Qt
    Physical chemistry Specific chemical reactions; reaction mechanisms Isomerization and rearrangement
  • 34.50.Lf
    Atomic and molecular collision processes and interactions Scattering of atoms, molecules, and ions Chemical reactions, energy disposal, and angular distribution, as studied by atomic and molecular beams
  • 82.20.Kh
    Physical chemistry Chemical kinetics Potential energy surfaces for chemical reactions
  • 31.15.Ar
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Ab initio calculations
  • YEAR: 1995

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (28)
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