Vibronic theory of the intramolecular cis-trans photoisomerization of complexes of divalent platinum

Journal Article · Sun Sep 01 04:00:00 EDT 1985 · Sov. J. Coordinat. Chem.; (United States)

OSTI ID:6419555

D'yachkov, P N

The mechanism of the cis-trans photoisomerization of square complexes with a d/sup 8/ configuration of the central atom has been studied from the point of view of the theory of the Jahn-Teller effect and the pseudo-Jahn-Teller effect. The investigation was carried out under the assumption that the photoisomerization takes place according to an intramolecular twisting mechanism. It has been noted that intramolecular twisting with a stable and an unstable intermediate should be distinguished. In the former case, the predominant reaction path is trans ..-->.. cis isomerization along a triplet term, which may be accompanied by reversible cis-trans isomerization through a singlet state. When the tetrahedral transition state is unstable, trans ..-->.. cis isomerization is forbidden, but the reverse reaction can take place with small quantum yields. The results obtained have been used to interpret experimental data for complexes of the Pt/sup II/L/sub 2/X/sub 2/ type.

• OSTI ID: 6419555
• Journal Information: Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 10:11; ISSN SJCCD
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
CATALYTIC EFFECTS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CONFIGURATION INTERACTION
COORDINATION NUMBER
DEFORMATION
DISTANCE
ENERGY-LEVEL TRANSITIONS
FUNCTIONS
HAMILTONIANS
INTERATOMIC DISTANCES
ISOMERIZATION
ISOMERS
JAHN-TELLER EFFECT
LATTICE VIBRATIONS
LIGANDS
MATHEMATICAL OPERATORS
MECHANICS
MOLECULAR ORBITAL METHOD
NUCLEAR DEFORMATION
PERTURBATION THEORY
PHOTOCHEMICAL REACTIONS
PHOTOSENSITIVITY
PLATINUM COMPLEXES
POTENTIALS
QUANTUM MECHANICS
QUANTUM OPERATORS
REACTION INTERMEDIATES
SENSITIVITY
TRANSITION ELEMENT COMPLEXES
WAVE FUNCTIONS
YIELDS