Formation and relaxation of excited states in solution: A new time dependent polarizable continuum model based on time-dependent density functional theory

PHYS 435

Marco Caricato, marco.caricato@yale.edu1, Benedetta Mennucci, bene@dcci.unipi.it2, Jacopo Tomasi, tomasi@dcci.unipi.it2, Francesca Ingrosso, fingross@gmail.com3, Roberto Cammi, chifi@ipruniv.cce.unipr.it4, Stefano Corni, corni.stefano@unimore.it5, and Giovanni Scalmani6. (1) Department of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520-8107, (2) Dipartimento di Chimica e Chimica Industriale, UniversitÓ di Pisa, Via Riorgimento 35, 56126 Pisa, Italy, (3) Departement de Chemie, Ecole Normale Superieure, 24 Rue Lhomond, Paris, 75231, France, (4) Dipartimento di Chimica Generale ed Inorganica, UniversitÓ di Parma, Parco Area delle Scienze, 43100 Parma, Italy, (5) Center of nanoStructures and bioSystems at Surfaces, INFM-CNR, Via Campi 231/A, Modena, 41100, Italy, (6) Gaussian Inc, 340 Quinnipiac St. Bldg 40, Wallingford, CT 06492
A novel approach to study the formation and relaxation of excited states in solution is presented within the integral equation formalism version of the polarizable continuum model. This approach uses the excited state relaxed density matrix to correct the time-dependent density functional theory excitation energies and it introduces a state-specific solvent response, which can be further generalized within a time dependent formalism. This generalization is based on the use of a frequency-dependent complex dielectric permittivity. This approach is here presented in its theoretical formulation and applied to the various steps involved in the formation and relaxation of electronic excited states of solvated molecules. In particular, vertical excitations (and emissions), as well as time-dependent Stokes shift and complete relaxation from vertical excited states back to the ground state, can be obtained as different application of the same theory.

Poster Session
7:30 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Physical Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006